Tese(mestrado) - Universidade Federal Do Rio Grande, Programa de Pós-graduação em Oceanografia Biológica, Instituto de Oceanografia, 2013. / Submitted by Cristiane Gomides (cristiane_gomides@hotmail.com) on 2013-11-18T12:52:36Z No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) / Approved for entry into archive by Angelica Miranda (angelicacdm@gmail.com) on 2013-11-18T19:07:50Z (GMT) No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) / Made available in DSpace on 2013-11-18T19:07:50Z (GMT). No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) Previous issue date: 2013 / Imagens de satélite da cor do oceano detectam intensas florações do fitoplâncton durante primavera e verão ao longo da quebra de plataforma Argentina, mas são escassas as medidas ópticas in situ na região. O objetivo geral desta tese foi investigar a variabilidade das propriedades ópticas das florações do fitoplâncton na quebra de plataforma Argentina e arredores. Entre 2006 e 2009, seis cruzeiros foram conduzidos com diversas medidas biológicas e físicas, incluindo medicões bio-ópticas, dentre as quais algumas inéditas na região. As seguintes medidas foram consideradas: coeficientes spectrais de absorção da luz pelo material particulado, que inclui o fitoplâncton e detritos; coeficiente de atenuação da luz pelo material particulado a 660nm; irradiância descendente e radiância ascendente da luz com alta resolução espectral, a partir das quais se obtém os coeficientes da atenuação difusa e a reflectância do sensoriamento remoto in situ; reflectância do sensoriamento remoto medida por satélite; concentração de clorofila-a total e fracionada por classes de tamanho do fitoplâncton estimada pelo método fluorimétrico; concentrações de clorofila-a e pigmentos acessórios do fitoplâncton, obtidas por HPLC; abundância taxonômica relativa do fitoplâncton estimada por CHEMTAX; e fator de tamanho celular do fitoplâncton estimado pelos espectros de absorção da luz pelo fitoplâncton. Grande variabilidade foi observada nos coeficientes de absorção, atenuação (e espalhamento) e atenuação difusa da luz para uma dada concentração de clorofila-a e vice-versa. Grande parte dessa variabilidade pôde ser explicada por variações no tamanho celular do fitoplâncton e, portanto, ao efeito “pacote”. A variabilidade nos espectros de reflectância do sensoriamento remoto (propriedade óptica aparente) medidos in situ revelou o fitoplâncton como componente dominante nas propriedades ópticas das florações na região. Porém, a variabilidade nos coeficientes específicos (i.e., normalizados por clorofila-a) de absorção e espalhamento (propriedades ópticas inerentes), devido a variações no tamanho celular do fitoplâncton, influenciou o desempenho de modelos bio-ópticos para estimar concentração de clorofila-a por satélite. As principais situações de composição taxonômica do fitoplâncton que ocorrem durante as florações na região (dominância por diatomáceas, haptofíceas, e com contribuições destes grupos e de outros, sem dominância) foram refletidas de forma coerente nos comportamentos espectrais de absorção da luz pelo fitoplâncton, indicando o potencial em discriminar as assembleias das florações na região através de dados ópticos. Particularmente, a identificação de dominância de diatomáceas e haptofíceas, a partir de um comprimento de onda, e também pelo fator de tamanho celular do fitoplâncton, que pode ser estimado por satélite, indica o potencial em identificar a dominância de tais grupos taxonômicos por sensoriamento remoto na região. / Satellite images usually detect intense phytoplankton blooms during spring and summer along the Argentina shelf break. Because in situ optical measurements are scarce in the region, six cruises were conducted from 2006 to 2009 to measure several physical, biological, and optical properties. Some of the bio-optical properties were gathered for the first time in the region. The aim of this thesis was to characterize the optical properties of phytoplankton blooms along the Argentina shelf break e adjacent areas. For this purpose, the following measurements and data were considered: light absorption coefficients of particulate material that includes phytoplankton and detritus; light attenuation coefficient of particulate material at 660 nm; hyperspectral downwelling irradiance and upwelling radiance, from which one obtains the vertical attenuation coefficients for downwards irradiance and upwards radiance and in situ reflectance of remote sensing; total and size-fractionated chlorophyll-concentration, estimated by fluorimetric method; concentrations of chlorophyll-a and accessory pigments of phytoplankton obtained by HPLC; relative taxonomic abundance of phytoplankton estimated by CHEMTAX; a cell size parameter for phytoplankton estimated from the phytoplankton absorption spectra. Large variability was observed for absorption coefficients of phytoplankton, scattering of particles and the vertical attenuation coefficients for downwards irradiance for a given chlorophyll-a concentration. Such variability could be largely explained by variations in cell size of phytoplankton and therefore the "package" effect, as indicated by the cell size parameter. The characterization of the variability in the remote sensing reflectance (apparent optical property) measured in situ revealed phytoplankton as the dominant component on the optical properties of algal blooms in the region. Nevertheless, the variability in absorption and scattering coefficients (inherent optical properties) due to variations in cell size of phytoplankton was shown to impact the performance of bio-optical models that relies on band reflectance ratios of remote sensing to retrieve chlorophyll-a from satellite. The main taxonomic composition of the phytoplankton blooms (dominance of diatoms, haptophytes, and mixed contributions of these and others groups, but with no dominance) was consistently reflected on the spectral shape of light absorption of phytoplankton. Our results indicate a potential to discriminate phytoplankton assemblages in the region through optical data. Particularly, the identification of diatoms or haptophytes using one wavelength or through a phytoplankton cell size parameter, which can be estimated from satellite, has a potential of identifying the dominance of such taxonomic groups from remote sensing in the region.

Este estudo reúne os principais resultados de fluorescência estática e resolvida no tempo sobre a interação da porfirina meso-tetrakis (4-metilpiridil), na forma de base livre (TMPyP) e complexada com Zn2+ (ZnTMPyP), com vesículas de fosfolipídio. Adicionalmente foram utilizadas as técnicas de potencial zeta e espalhamento de luz dinâmico (DLS, do inglês \"dynamic light scattering\"). As vesículas de fosfolipídio foram formadas por dois conjuntos de fosfolipídios: saturados e insaturados. O primeiro grupo é formado pela mistura dos fosfolipídios zwiteriônico 1,2-dipalmitoil-sn-glicero-3-fosfocolina (DPPC) e aniônico 1,2-dipalmitoil-sn-3-glicero-[fosfo-rac-(1- glicerol)] (DPPG), a diferentes razões molares. Os estudos utilizando tais sistemas foram realizados abaixo (25oC) e acima (50oC) da temperatura de transição de fase gel-líquido cristalino destes fosfolipídios (~ 41oC). O segundo grupo é formado pela mistura dos fosfolipídios zwiteriônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfocolina (POPC) e aniônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfo(1-rac-glicerol) (POPG). Como a transição de fase destes dois fosfolipídios ocorre a temperaturas negativas, todos os experimentos foram realizados a 25oC (vesículas no estado líquido cristalino). Todos os sistemas foram preparados através do método de extrusão para a obtenção de vesículas grandes unilamelares (LUV, do inglês \"large unilamellar vesicles\"). As análises dos dados de fluorescência indicaram que a atração eletrostática entre os substituíntes (positivamente carregados) das porfirinas TMPyP e ZnTMPyP e o grupo das cabeças polares (camada de Stern) das vesículas de fosfolipídio desempenha um papel fundamental na associação da porfirina. A distribuição da TMPyP entre o meio aquoso (tampão) e as vesículas de fosfolipídio foi evidenciada pela coexistência de um tempo de vida de fluorescência mais curto (~ 5 ns) e outro mais longo (~ 9-11 ns), respectivamente. Baseado nos valores das constantes pré-exponenciais, estudos adicionais mostram que a distribuição acima é afetada pela concentração de sal na solução. Os resultados de supressão de fluorescência com o supressor iodeto de potássio (KI) indicaram que ambas porfirinas estão localizadas, preferencialmente, na região da camada de Stern. Este resultado foi confirmado pelos estudos de potencial zeta e de DLS, os quais mostraram uma neutralização parcial das cargas negativas na superfície das vesículas devido à associação da porfirina. / This study presents time-resolved and steady-state fluorescence results on the interaction of the meso-tetrakis (4-methylpyridil) porphyrin, in free base form (TMPyP), and complexed with Zn2+ (ZnTMPyP), with phospholipid vesicles. Zeta potential and dynamic light scattering (DLS) techniques were also used. Phospholipid vesicles were formed by two phospholipid systems: saturated and unsaturated. The first group is a mixture of zwiterionic dipalmitoyl-sn-glycero-3-phosphocoline (DPPC) and anionic 1,2-dipalmitoyl-sn-3-glycero-[phospho-rac-(1-glycerol)] (DPPG) phospholipids, at different molar ratios. Measurements were performed bellow (25oC) and above (50oC) the main gel-liquid crystalline phase transition temperature (~ 41oC). The second group is constituted by a mixture of zwiterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocoline (POPC) and anionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho(1-rac-glycerol) (POPG) phospholipids, at different molar ratios. Since the gel-liquid crystalline phase transition of these phospholipids occurs at a very low temperature value, all experiments were performed at 25oC (liquid crystalline state vesicles). All phospholipid systems were prepared through the extrusion method in order to obtain large unilamellar vesicles (LUV). The fluorescence data analyses indicated that the electrostatic attraction between the porphyrin substituents (positively charged) and the polar head groups of the phospholipid vesicles (Stern layer) plays an important role on the porphyrin binding affinity. The distribution of TMPyP between the aqueous medium (buffer) and the phospholipid vesicles was characterized by the coexistence of a shorter (~ 5 ns) and a longer (~ 9-11 ns) fluorescence lifetimes, respectively. Based on the pre- exponential values, additional time-resolved experiments showed a redistribution of the porphyrin at increasing salt concentration. The quenching studies, using potassium iodide (KI) as quencher, indicated that both TMPyP and ZnTMPyP are preferentially located at the Stern layer region. This result is in agreement with the zeta potential and DLS findings, which demonstrated a partial neutralization of the negative charges at the vesicle surface due to the porphyrin association.

Orientador: Telma Teixeira Franco / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-02T19:11:38Z (GMT). No. of bitstreams: 1 Todorovic_Zoran_M.pdf: 2109964 bytes, checksum: a9300d59d70b5fdcbb2831ea8b7e1899 (MD5) Previous issue date: 2002 / Resumo: A biocompatibilidade, biodegradabilidade e o fato de ser um polimero catiônico bioadesivo fazem a quitosana um material atrativo para inúmeras aplicações na área biotecnológica, agrícola, farmacêutica e médica. As quito sanas com massas molares baixas e os oligômeros têm maiores perspectivas nas últimas duas áreas. O objetivo deste projeto de pesquisa foi a obtenção de polimeros com massa molar média reduzida devido à ação da enzima papaína. Empregando papaína livre e em forma imobilizada a redução da massa molar da quito sana foi estudada. Quitina foi utilizada como suporte para imobilização da papaína e para imobilização da proteína modelo albumina de soro bovino. Experimentos com todos estes materiais foram realizados para estudar os efeitos da modificação da quito sana. Os experimentos foram conduzidos em reatores batelada com pH e temperatura controlados. Soluções da quito sana (1 %) foram preparadas utilizando ácido lático ou ácido acético para solubilização. Duas técnicas para determinação da massa molar da quito sana foram utilizadas. Em primeiro lugar, a visco simetria foi empregada sendo esta a técnica mais comum para investigação de redução da massa molar. Redução da viscosidade de soluções de quitosana foi associada à diminuição da massa molar média. Outro método utilizado para a determinação de massas molares foi a cromatografia de permeação em gel, que é considerado um método relativo de determinação de massa molar, pois necessita de padrões dos polimeros para a construção de uma curva padrão. A massa molar determinada por estes dois métodos é dependente do tamanho da molécula (diâmetro). O método absoluto de determinação da massa molar com detector de espalhamento de luz também foi utilizado. Este detector conectado on-line com cromatografia de permeação em gel fornece dados absolutos da massa molar média. Luz espalhada de diferentes partes da molécula do polimero em diferentes ângulos geram o valor correto da massa molar sem utilização dos padrões. Os resultados mostraram o efeito superior na redução da massa molar utilizando papaína em comparação com outros materiais utilizados. Esta redução da massa molar média é rápida e acentuada nos primeiros minutos da reação, em comparação com a continuação do processo / Abstract: Biocompatibility, biodegradability and the fact of being bioadhesive polycationic polymer make chitosan an attractive material for various applications in agricultural and biotechnological, pharmaceutical and medical fields. Chitosans with lower molecular weights and oligomers OOve major perspectives in the last two fields. An objective of this project of research was the production of polymers with reduced molecular weight due to the action of enzyme papain. Applying papain in the free and immobilized form the reduction of molecular weight of chitosan was studied. Chitin was used as a support for the immobilization of papain and for the immobilization of model protein bovine serum albumin. Experiments with all these materiais were realized to study the effects of modification of chitosan. Experiments were run using batch reactors at controled pH and temperature. Chitosan solutions (1 %) were prepared using lactic acid or acetic acid for solubilization. Two different techniques were used for determination of molecular weight of chitosan. First viscosimetry was applied as the most common technique used for investigation of reduction of molecular weights. Reduction of viscosity of chitosan solutions is associated with the reduction of molecular weight. The other method used for determination of molecular weights is gel permeation chromatography toot is considered a relative method of determination of molecular weights as it requires polymeric standards for the construction of the standard curve. Molecular weight determined by these two methods is dependant of the molecular size (diameter). Absolute method of determination of molecular weights through measurements with detector of light scattering was aIso applied in this studies. This detector connected on-line with gel penneation chromatography provides us with the absolute molecular weights. This method does not require standards measuring the light scattered from different parts of the polymeric molecule in different angles generating in this way the correct value of molecular weight. Results show the superior effect of papain on the reduction of molecular weight compared to the other materiais used. This reduction of molecular weight is fast, pronounced in the :fust minutes of the reaction in comparison with the continuation of the process / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

La connaissance de la dynamique interne du noyau d’une cellule vivante semble essentielle pour la compréhension du fonctionnement des cellules eucaryotes. Ainsi, depuis plus d'une quinzaine d’année, de nombreuses études ont été menées pour sonder cette dynamique. Le projet de recherche de cette thèse s’est inscrit dans cette problématique. Nous avons monté une expérience originale de diffusion dynamique de la lumière pour sonder la dynamique interne du noyau d’une cellule. Le principe est simple, nous faisons passer un faisceau laser à travers le noyau d’une cellule et nous détectons les variations temporelles de l’intensité lumineuse diffusée. Les signaux obtenus sont complexes, non stationnaires, avec plusieurs échelles de temps. Une partie importante du travail de thèse a consisté à trouver une manière fiable de les analyser pour en extraire la dynamique interne du noyau ; nous arrivons à sonder cette dynamique sur quasiment 7 ordres de grandeurs (10-5 – 40 s). En utilisant ce montage et les techniques de traitement du signal qu’on a développé, nous avons étudié la dynamique interne du noyau de cellules issues de deux lignées humaines (SHEP et HeLa) au cours de leur cycle cellulaire. Nous observons des différences notables entre les phases G1, S et G2 et nous pouvons voir les gammes de temps affectées par le changement de phase du cycle cellulaire. Ensuite, nous avons étudié la dynamique du noyau de cellules (SHEP et HeLa), en phase G1, en présence d’une drogue cytobloquante dans le milieu de culture. Nous avons aussi étudié l’effet de la température. Pour des cellules en phase G1, nous avons baissé la température de 37°C à 25° C. Nous avons pu suivre l’évolution de la dynamique lors du refroidissement et à 25°C. Enfin, nous avons étudié la dynamique du noyau des cellules SHEP et HELA fixées. / The knowledge of the internal dynamics of a living cell nucleus appears essential for the comprehension of the activity of eukaryotic cells. Therefore, for the last fifteen years, many studies have been conducted to probe this dynamics. The research project of this thesis is a part of this issue. We set up an original experience of dynamic light scattering to probe the internal dynamics of a cell nucleus. The principle is simple, we pass a laser beam through the nucleus of a cell and we detect the temporal variations of the scattered light intensity. The signals obtained are complex, non-stationary, with different time scales. An important part of the thesis was to find a reliable way to analyze them to extract the internal dynamic of the nucleus; we can probe this dynamic on almost 7 orders of magnitude (10-5 – 40 s). By using this experience and the signal procession techniques that we developed, we studied the internal dynamics of the nucleus of two human cell lines (HELA and SHEP) in their cell cycle. We observe significant differences between the G1 phase, S and G2 and we can see the time ranges affected by phase change of the cell cycle. Next, we have studied nucleus dynamics of cells (SHEP and HELA), in the G phase, in the presence of cytobloquante drug in the culture environment. We also studied the effect of temperature. For cell in G1 phase, we lowered the temperature of 37°C to 25° C. We were able to follow the changing dynamics during the cooling and at 25°C. Finally, we have studied nucleus dynamics of fixed SHEP and HELA cells.

La poudre de boehmite, précurseur de l’alumine utilisée pour la production de supports catalytiques variés, est produite suite à une étape de séchage par atomisation. Cet oxyhydroxyde d’aluminium est composé de particules anisotropes chargées. Ces dernières années, il a été ont montré que les propriétés physico-chimiques des suspensions avaient une influence sur les caractéristiques des poudres. La morphologie des grains (sphère creuse, tore…) ainsi que les propriétés des poudres (dispersibilité, résistance mécanique…) peuvent être modifiées en jouant sur les caractéristiques des suspensions.Ce travail de thèse porte sur la compréhension des liens entre les propriétés physico-chimiques et rhéologiques de suspensions de deux boehmites industrielles et les propriétés des grains obtenus après séchage. Dans une première partie, nous avons caractérisé les particules en suspension de ces deux boehmites grâce à une approche multi-technique (SAXS, DLS, MET). Une étude rhéologique des suspensions obtenues par stress osmotique a ensuite permis de construire précisément le diagramme de phase de ces deux boehmites dans le plan force ionique – fraction volumique. La diffusion des rayons X aux petits angles et la diffusion dynamique de la lumière ont été utilisées pour déterminer l’organisation structurale des suspensions. Enfin, des expériences de séchage suivies optiquement et par micro-tomographie X ont été réalisées sur des suspensions de boehmite afin d’étudier l’impact de la concentration et de la force ionique sur l’évolution de la goutte au cours du séchage. / In the catalyst supports industry, one important step of alumina powder production is the spray-drying of boehmite suspensions. This aluminium oxyhydroxyde is often used as precursor for various types of alumina catalyst supports. Boehmite is composed of anisotropic particles bearing an electric charge. In the past decade, it has been shown that the properties of the dry powder depend not only on the drying conditions but on physico-chemical properties of the sprayed suspensions. For instance, different grains morphologies (doughnut-shaped grains, hollow spheres,…) as well as various dry grains properties (textural properties, mechanical resistance,…) may be obtained by tuning the physico-chemical properties of the suspension.This study focus on the understanding of the links between the physico-chemical properties of suspensions of two industrial boehmites and the characteristics of the final dry grain. Since these two boehmites were not well-known, the first step of the study was to characterize boehmite particles present in suspension thanks to a multi-technical approach. A rheological study was performed on boehmite suspensions obtained thanks to osmotic stress to build precisely the phase diagrams of the both boehmites according to the system of ionic strength vs. volume fraction. Small angle X ray scattering and dynamic light scattering were used to investigate the existence of an orientational order of boehmite particles in suspension. Finally, drying experiments of boehmite suspensions were conducted on an optical set-up and on fast micro-tomography X, to examine the impact of both concentration and ionic strength on the evolution of the droplet during drying.

Abstract The amount of printing ink in a pulp suspension produced from recovered paper and its impact on overall brightness is commonly estimated from the reflectance-based ink content measured at a wavelength of 700 nm or 950 nm. The method uses a light scattering coefficient that can be measured from a slightly translucent test medium, i.e. of an opacity less than 97%. This is the case with machine-made papers in most instances. Alternatively, suitable opacity can be achieved by preparing a standard low-grammage sheet on a wire screen, but this results in poor retention of fibre fines, mineral fillers and printing inks, which is especially detrimental to ink measurement when the pulp suspension contains substantial amounts of printing inks. Hence opaque pads are often prepared on filter paper to achieve high retention. Unfortunately their high opacity prevents measurement of the light scattering coefficient, and thus a constant coefficient must be used for the determination of ink content. The aim of this thesis was to clarify the effects of retention and fine material changes on the light scattering coefficient in ink content measurement. The results showed that the light scattering properties of pulp in the wavelength region used for ink content analysis do not remain constant when the fine material content varies. The grade of the recovered paper, hyperwashing and flotation alter the fine material content and thus affect the light scattering. Printing ink also affects light scattering, but its practical impact is smaller than that of fibre fines and mineral fillers. The light scattering coefficient used for each ink content measurement needs to be representative, otherwise a systematic bias in ink content measurements may result from changes in the nature of the fine material and in its content. It is recommended that the light scattering coefficient should be measured in order to avoid this. The measurement should preferably be performed from a low-grammage sheet prepared on filter paper, as this ensures high retention and a measured value that represents better the initial state of the pulp suspension. / Tiivistelmä Mustepitoisuusmittaus perustuu hajaheijastukseen joko 700 nm tai 950 nm aallonpituudella ja sitä käytetään usein arvioitaessa keräyspaperista valmistetun massasuspension soveltuvuutta painopaperien valmistukseen ja painomusteen vaikutusta massan vaaleuteen. Mustepitoisuuden mittauksessa käytetään valonsirontakerrointa, joka voidaan mitata hieman läpikuultavasta näytteestä eli näytteen opasiteetin on oltava pienempi kuin 97 %. Tämä opasiteettiraja toteutuu useimmiten paperikoneella tehdyille painotuotteille. Riittävän alhainen opasiteetti saavutetaan myös valmistamalla standardin mukainen matalaneliömassainen arkki viiralle, mutta tämä johtaa kuitumaisten hienoaineiden, mineraalisten täyteaineiden ja painomusteiden alhaiseen retentioon. Matala retentio on erityisen haitallinen piirre mustemittauksen kannalta massoilla, jotka sisältävät huomattavia määriä painomusteita. Siten usein valmistetaan läpikuultamattomia arkkeja suodatinpaperin päälle, joiden retentio on korkea. Korkeasta opasiteetista johtuen näistä arkeista ei voida määrittää valonsirontakerrointa, jolloin mustepitoisuuden määritys perustuu vakiokertoimeen. Tämän väitöskirjan tavoitteena oli selvittää retention ja hienoaineiden muutoksien vaikutuksia valonsirontakertoimeen ja mustemittaustulokseen. Tutkimuksen tulokset osoittivat että valonsirontakerroin, joka mitataan mustepitoisuuden yhteydessä, ei pysy vakiona hienoainepitoisuuden muuttuessa. Hienoainepitoisuuteen ja siten valonsirontakertoimeen vaikuttavat keräyspaperin laji, hyperpesu ja vaahdotus. Myös painomuste vaikuttaa valonsirontakertoimeen, mutta käytännössä vaikutuksen suurusluokka on pienempi kuin hieno- ja täyteaineilla. Mustepitoisuuden määrityksessä käytetyn valonsirontakertoimen on oltava edustava, muutoin arvot voivat olla systemaattisesti virheellisiä hienoainemäärän tai laadun muuttuessa. Virheen välttämiseksi olisi suositeltavaa määrittää valonsirontakerroin mustepitoisuusanalyysin yhteydessä. Tämä olisi mahdollista tehdä suodatinpaperin päälle valmistetusta matalaneliömassaisesta arkista, jolloin saavutetaan korkea retentio ja näin mitattu arvo edustaa paremmin massasuspension alkuperäistä tilaa.

Master of Science / Department of Mechanical and Nuclear Engineering / Steven J. Eckels / Christopher M. Sorensen / Large specific surface areas and high concentrations of reactive edge and defect sites make NanoActive™ metal oxide powders ideal chemical adsorbents. These powders are dispersed in aerosol form to remediate toxic wastes and neutralize chemical and biological warfare agents. In the destructive adsorption of toxic chemicals, effective application requires particles be as small as possible, thus, maximizing surface area and number of edge and defect sites. Other applications, e.g. smoke clearing, require particles be large so they will settle in a timely manner. Ideally, particle size control could be engineered into powder dispersion devices. The purpose of this study was to explore particle cohesion and aerodynamic deaggregation mechanisms to enhance the design of powder dispersion devices. An aerosol generator and four experimental nozzles were designed to explore the most commonly referenced deaggregation mechanisms: particle acceleration, particles in shear and turbulent flows, and particle impaction. The powders were then dispersed through the nozzles with increasing flow rates. A small angle light scattering device was used to make in situ particle size measurements. The nozzle designed for impaction deaggregated the NanoActive™ MgO particles to a lesser degree than the other three nozzles, which deaggregated the particles to a similar degree. Flows in three of the four nozzles were simulated in a commercial computational fluid dynamics package. Theoretical particle and aggregate stresses from the literature were calculated using simulated data. These calculations suggest particle acceleration causes internal stresses roughly three orders of magnitude larger than shear and turbulent flows. These calculations, coupled with experimental data, lead to the conclusion that acceleration was the most significant cause of particle deaggregation in these experiments. Experimental data also identified the dependence of deaggregation on primary particle size and agglomerate structure. NanoActive™ powders with smaller primary particles exhibited higher resistance to deaggregation. Small primary particle size was thought to increase the magnitude of van der Waals interactions. These interactions were modeled and compared to theoretical deaggregation stresses previously mentioned. In conclusion, deaggregation is possible. However, the ideas of particle size control and a universal dispersion device seem elusive considering the material dependent nature of deaggregation.

Ce travail est consacré à l'étude, par des techniques originales de diffusion dynamique de la lumière, de la dynamique lente de deux systèmes colloïdaux modèles. On a utilisée une technique de Corrélation Résolue dans le Temps (TRC) et des simulations numériques pour sonder, sur une grande plage de concentrations et sur sept décades en temps de relaxation, la dynamique d'un système de sphères dures colloïdales approchant de la transition vitreuse. A faible fraction volumique les temps de relaxation peuvent être représentés par une loi de puissance critique comme prévu par la Théorie de Couplage des Modes (MCT). A des concentrations élevées le temps de relaxation augmente selon une inattendue loi exponentielle critique avec une fraction volumique critique supérieure à celle prévue par MCT. L'étude des fluctuations de la dynamique confirme la présence d'un régime de dynamique activée: ce scénario est le même que l'on retrouve pour les systèmes vitreux moléculaires. Le deuxième sujet étudié est le comportement d'une suspension de colloïdes attractifs soumis à la contrainte gravitationnelle. Initialement, des agrégats de particules sédimentent en formant un gel sur le fond de la cellule. Les techniques spéciales employées nous ont permis de mesurer l'évolution des profils de concentration, des profils de vitesse et la dynamique locale dans la phase gel: la sédimentation peut être complètement décrite par le taux de déformation locale qui permet aussi une remise à l'échelle de la dynamique locale. Le rôle de la friction aux parois des cellules a été sondé par des expériences de polarimétrie et par la résolution numérique d'un modèle poroélastique pour la sédimentation du gel. / We investigated, using original light scattering techniques, the slow dynamics of two different model colloidal systems. We used a Time Resolved Correlation (TRC) technique and numerical simulations to study the dynamics of systems of colloidal hard spheres over a broad range of densities and seven decades in relaxation time. At low volume fraction the equilibrium relaxation time is described by the algebraic divergence predicted by mode-coupling theory (MCT). At higher density the relaxation time increases with an unexpected critical exponential form, whose the critical volume fraction is much larger then the MCT singularity. The fluctuations of the dynamics confirm the presence of an activated regime, as founded in molecular glass formers close to the glass transition. The second research subject concerns the behaviour of suspensions of attractive colloidal particles under gravitational stress. Initially, clusters fall forming a gelled deposit at the cell bottom. Our apparatus allows us to follow over time the concentration profile, the velocity profile and the local dynamics in the gel phase: the settling may be fully described by the local strain rate and dynamics exhibits remarkable scaling properties when time is normalized by strain rate. The role of the solid friction at the cell walls has been investigated by polarimetry experie nces and solving numerically a poroelastic model of gel sedimentation.

L’interaction entre la lumière et un nuage atomique désordonné et dilué donne lieu à des effets de cohérence collectifs dus à l’interaction des dipôles induits par le biais du champ lumineux. L'influence de tels effets de cohérence en diffusion multiple suscite beaucoup d’intérêt. Nous présentons deux modèles théoriques qui décrivent ces effets de cohérence dans différents régimes de diffusion. Le traitement du processus à travers un développement en ordres successifs de diffusion nous permet de mettre en évidence la contribution du premier et second ordres ainsi que l'interférence entre les champs diffusés qui en résultent. Dans le régime de diffusion multiple, nous montrons que la force de pression de radiation n'est pas une bonne observable pour sonder les effets coopératifs. Par ailleurs, nous mettons en évidence une surprenante cohérence de phase qui suggère une persistance des effets coopératifs en diffusion multiple. Cela pourrait être le résultat d'une synchronisation entre les dipôles atomiques couplés. Dans une deuxième partie, nous étudions l'effet d'une déformation de l'algèbre de Weyl-Heisenberg sur l'intrication des états cohérents. Une telle approche permet de décrire la décohérence dans des systèmes quantiques intriqués soumis à une perturbation extérieure. Nous construisons des états cohérents déformés intriqués et nous calculons leur concurrence. Nous montrons que la déformation de l'algèbre pourrait avoir un impact non négligeable sur la qualité de l'intrication bipartie des états cohérents, si cette dernière n'est pas maximale. / This work is devoted on the one hand to the investigation of coherence effects in multiple scattering of light by an atomic cloud and on the other hand to the entanglement of a deformed coherent state. The interaction between light and a dilute disordered atomic cloud gives rise to collective coherent effects due to the interaction of the induced dipoles via the external field. The behavior of such coherent effects in multiple scattering regime is an important question for various physical systems. We present two theoretical models describing those coherence effects in different scattering regimes. The scattering order expansion treatment of light scattering allows us to highlight the role of the first and second scattering orders as well as the interference between the resulting scattered fields. In the multiple scattering regime we show that the radiation pressure force is not a good observable to probe cooperative effects. Furthermore, we discover a surprising phase coherence that hints that collective effects may survive in multiple scattering regime. That could be due to a synchronization between the induced atomic dipoles. In a second part, we study the effect of an algebra deformation on entangled coherent states. Such an approach allows to describe decoherence in perturbed entangled quantum systems. We construct a deformed coherent state and calculate their concurrence. We show that algebra deformation could have a non negligible impact on bipartite entangled coherent states if those later are not maximally entangled.

This thesis deals with the study of preparation and characterization of hyaluronan-micelle aggregates. The theoretical part deals with drug delivery systems, characterization of used materials and methods especially fluorescence spectroscopy, dynamic light scattering and turbidimetry. Methods of determination of measured data are summarized in the experimental section. The result section is divided into two subsections dedicated to different preparation methods of hyaluronan-surfactant complexes. Induced aggregates of hyaluronan with Septonex are characterized in terms of their origin and stability, and the results are compared with previously studied surfactants CTAB. In the second part are discussed so-called decorated micelles, their formation, properties and stability.