Ce manuscrit de thèse de doctorat présente les travaux de développement d’un granulomètre optique pour la caractérisation de suspensions de nano et microparticules individuelles ainsi que d’agrégats. La mesure repose sur l’analyse suivant différents angles de la diffusion statique et dynamique de l’échantillon placé dans une cuve spectrophotométrique cylindrique. Il intègre différentes solutions originales telles qu’un éclairage par un faisceau laser de forte ellipticité, une détection sous le plan de diffusion conventionnel et l’utilisation d’une méthode de post-traitement qualifiée de « filtre quasi-statique ». Ces solutions permettent d’éliminer l’essentiel des problèmes liés aux réflexions spéculaires et diffuses de la cuve d’analyse, de même que les variations des dimensions du volume de mesure avec l’angle de diffusion et les cas de désalignement même léger du système goniométrique. Les signaux mesurés sont inversés avec des méthodes d’estimation de paramètres. Pour les particules sphériques, le problème direct est résolu avec la théorie de Lorenz-Mie. Pour les agrégats, il l’est avec un modèle d’agrégat fractal, des approximations par dipôles discrets ou Rayleigh-Gans-Debye. Les performances de cet instrument, de conception volontairement simple et robuste, ont été testées avec succès sur des nano et micro suspensions diluées, monomodales et bimodales, de latex et silice colloïdale, de même que des agrégats de particules aciculaires et sphériques. Il permet de caractériser la taille, la morphologie et la concentration absolue de particules dans la gamme de taille 20nm-2µm. / This PhD thesis manuscript presents the work conducted to develop an optical particle siz-ing instrument for the characterization of individual nano and microparticles, as well as their aggregates, in liquid suspensions. The measurement is based on the multi-angular analysis of the static and dynamic light scattering of a sample into a cylindrical spectrophotometric cell. This instrument integrates various innovative solutions such as an illumination by a high ellipticity laser beam, a detection under the conventional scattering plane and a post-processing method operating as a quasi-static filter. These solutions make it possible to elim-inate most of the problems associated with the specular and diffuse reflections of the analy-sis cell, as well as the harmful variations of the probe volume dimension with the detection angle and in case of a slight misalignment of the system. The signal inversion is performed with parameters estimation methods. For spherical particles, the direct problem is solved with the Lorenz-Mie theory. For aggregates, it is solved with a fractal aggregate model and approximations based on discrete dipoles or Rayleigh-Gans-Debye theories. The perfor-mance of this instrument, of a deliberately simple and robust design, has been successfully tested on dilute nano and micro suspensions of latex and colloidal silica, mono and bimodal, as well as aggregates of acicular and spherical particles. It allows to characterize the size, the morphology and the absolute concentration of particles in the size range 20nm-2μm.

The thesis is focused on the research of stability of controlled drug release systems based on a blend of plasticized starch/polycaprolactone (TPS/PCL) that served as a carrier. Antibiotic vancomycin was used as a model drug, and its release from TPS/PCL pellets into aqueous environment was followed by UV-spectroscopy and the obtained time dependences were treated by a simple kinetic model. Moreover, the simultaneous release of starch particles to the surrounding liquid phase was studied by static and dynamic light scattering as well as transmission electron microscopy (TEM) in order to obtain information on the stability of biodegradable matrix and on the structure of the products of the pellet decomposition on a nanoscale level. Key words: vancomycin, starch, drug delivery system, polycaprolactone (PCL), particle release, dynamic light scattering (DLS), static light scattering (SLS)

Biologiska läkemedel har under det senaste århundradet utökats, och under de senaste 25 åren så har proportionen av godkända biologiska läkemedel har ökat för behandlingen av sjukdomar, vaccin, och diagnostik. Det finns flera olika mekanismer för protein aggregering, och en av dessa är seeding, vilket innebär aggregering inducerat av tillsatta aggregat eller förekomsten av strukturförändringar i proteinet. I detta examensarbete har två terapeutiska proteiner, Somatropin och en monoklonal antikropp, studerats i form av aggregering. Denna studie har utförts genom att värma en del av proteinlösningen för att bilda aggregat och strukturförändrat protein, och sedan blanda detta med nativt protein till olika volymprocent. Dessa lösningar förvarades i olika temperaturer, 4°C, RT och 40°C för att undersöka temperaturberoendet. Med Dynamic Light Scattering (DLS) mättes storleksfördelningen och medelstorleken på proteinet, vilket visade att de seedade proverna ökade i medelstorlek med tiden. Detta indikerar att seedingen inducerade aggregering med tiden. / Biological pharmaceuticals have expanded their use over the last decade, and during the recent 25 years, the proportion of approved biologics has increased for the treatment of diseases, vaccines, and diagnostics. There are several aggregation mechanisms, and one is seeding, i.e., aggregation induced by pre-formed aggregates or the presence of conformational changed proteins. In this master thesis, two therapeutic proteins, Somatropin and one monoclonal antibody have been studied in terms of aggregation. The study has been performed by heating a part of a protein solution to induce aggregation and mixing this with native protein in different volume percentages. These were stored in different temperatures, 4°C, RT, and 40°C, to investigate the temperature dependence. With Dynamic light scattering (DLS), the size distribution and the average-sized particles were measured. This showed that there was a growth of average size in the seeded samples with time. This indicates that the seeding induced aggregation with time.

No description available.

Prolongement central de la sclère, la cornée est la couche la plus externe de l'œil. Elle laisser pénétrer la lumière dans le globe oculaire grâce à sa propriété de transparence. Cette transparence repose sur une structure très organisée du tissu, maintenue en équilibre physiologique. Lorsque cet équilibre est rompu, notamment suite à une augmentation anormale de son taux d'hydratation et au développement d'un œdème, l'épaisseur du tissu augmente et il tend à s'opacifier. Lorsque l'œdème devient trop important, il est nécessaire de procéder à une greffe. Les cornées destinées à la greffe sont triées dans des banques de tissus, et sont en particulier soumises à une évaluation qualitative de leur transparence. Cette thèse s'inscrit dans le cadre d'un projet visant à étudier les propriétés de diffusion de greffons cornéens humains, afin d'améliorer l'évaluation quantitative de leur transparence en banque des tissus ou de mieux paramétrer les lasers de découpe lors des greffes de cornées, dont les performances sont altérées à cause du phénomène de diffusion. Le comportement diffusant de la cornée est mesuré dans l'espace réfléchi, afin d'évaluer à terme la possibilité d'une caractérisation in vivo. Conjointement à la mesure de diffusion, une imagerie du volume de la cornée est réalisée grâce à un dispositif de tomographie de cohérence optique apportant une caractérisation de la structure microscopique du tissu. L'œdème et son développement sont ainsi caractérisés par l'analyse de la diffusion du tissu, de sa transparence et des hétérogénéités à l'échelle du micron. / Along with the crystalline lens, the cornea is the unique tissue being transparent in the human body. With a transmission coefficient over 90% in the visible spectrum, the main function of the cornea is to transmit the light inside the eye. This property is due to an absence of blood vessels and a very regular organization of the corneal bulk. In the case of an edema development, the cornea swells because of an abnormally high hydration. This involves a disorganization of its internal structure and an increase of the light scattering, leading to cornea haziness. When the edema is too critical, a graft is then required. In tissue banks, several criteria, such as the evaluation of the transparency, are considered in order to choose only the tissues eligible for corneal transplantation. This thesis aims to study the scattering properties of human corneal grafts in order to improve transparency evaluation in tissue banks or to lead to a better calibration of laser cuts during surgery procedure. A characterization of the scattering properties of the tissues is performed in the reflective half-space. Indeed, backscattering characterization could be used in in-situ conditions. Moreover, 3D images of the bulk of the cornea are performed using a Optical Coherence Tomography set-up. Edema developement is studied through the analysis of the scattering behaviour and of the microscopic structure of the graft. Scattering properties and microstructure are linked together through the use of an electromagnetic modelling. Maxwell's equations are solved using Born approximation, and a numerical method was adapted to perform those calculations in the case of the cornea.

Neste trabalho, construímos um arranjo óptico para realizar medidas de espalhamento de luz dinâmico (Dynamic Light Scattering - DLS). Após o processo de montagem, o experimento foi calibrado por meio de soluções padrão de nanoesferas de poliestireno dispersas em água deionizada. Após a calibração, investigamos sistemas mais complexos como cristais líquidos nemáticos uniaxias, bem como misturas ferronemáticas. A primeira etapa dos estudos teve como objetivo investigar o comportamento das difusividades dos modos hidrodinmicos splay e twist, em função da concentração iônica das misturas. As amostras preparadas se diferenciavam apenas pela quantidades de sal em suas composições. Observamos um aumento em Dsplay e diminuição de Dtwist com o aumento na concentração de sal. Esses efeitos são multifatoriais e podem estar relacionados à blindagem eletrostática intermicelar, favorecendo a aproximaao entre micelas vizinhas. O efeito de backflow também é um fenômeno relevante que minimiza os efeitos dissipativos e está associado as distorções de splay. Por fim, foram realizadas medidas de DLS em misturas ferronemáticas liotrópicas uniaxiais, com o objetivo de investigar o comportamento das difusividades dos modos hidrodinâmicos em função da concentração de nanopartículas magnéticas (ferrofluido FF). O alinhamento do diretor é bastante favorecido com a presença das nanopartículas, como previsto na literatura [32]. Além disso, em baixas concentrações (< 10^13 grãos/mL) as nanopartículas não interferem nos espectros de autocorrelação, sendo possível observar as flutuações orientacionais do diretor nemático. Dessa forma, a incorporação de grãos magnéticos auxiliou nas medidas de DLS, principalmente no que diz respeito à seleção dos modos hidrodinâmicos. Os resultados mostraram que, em fase NC , as difusividades Dsplay e Dbend diminuíram com o aumento da concentração de FF. Por outro lado, a difusividade Dtwist praticamente não foi afetada com a incorporação de FF. No entanto, na fase ND, foi possível observar quedas nos valores de Dsplay e Dtwist , comparando com a mistura sem FF (Nd3). / In the present dissertation we made a Dynamic Light Scattering (DLS) experimental setup as well as their clalibration. We use standard aqueous solution with polystyrene nanospheres, with 20 nm and 200 nm of mean diameter, for system calibation. After this process we investigated more complex systems as uniaxial lyotropic liquid crystals mixtures and ferronematic samples. Firstly, we investigate the behaviour of hydrodynamic modes as a function of ionic concentration. The experiments showed that D splay increases and D twist decreases when ionic concentration increases. There are many factors around this behaviour, one of them is the electrostatic shielding forming between nearby micelles that may favours the approximation between tham. The backflow effect also is a relevante phenomenon that minimize the viscous dissipation process of splay distortion. This effect tends to increase with ionic concentration. We also investigated the hydrodynamic behaviour of uniaxial lyotropic mixtures doped with magnetic nanoparticles (ferrofluid - FF). They were characterized by DLS measure-ments to investigated the role of dopping concetration on splay, twist, and bend distortions. According to our results the nanoparticles favours the director alignment by magnetic field as we can found in the literature [32]. Thus, the DLS measurements had been favored by addition of magnetics grains, particularly with regard to the selection role of hydrodynamic modes. Moreover, we have seen that the director relaxation process is not abruptly affected with incorporation of nanoparticles, at low quantities (< 10^13 grain/mL). In NC phase, Dsplay and Dbend tends to decreases when the FF concetrations increases. However the behavior of Dtwist is not completly clear. In ND phase, the addition of nanoparticles further decreases Dsplay and Dtwist , comparing with the free nanoparticles sample (Nd3).

Made available in DSpace on 2014-12-17T15:41:55Z (GMT). No. of bitstreams: 1 WildsonAM_DISSERTPPGQ.pdf: 2126383 bytes, checksum: 6a1a9e8b2c55caac2fbd3fb938bff756 (MD5) Previous issue date: 2011-07-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Gels consist of soft materials with vast use in several activities, such as in pharmaceutical industry, food science, and coatings/textile applications. In order to obtain these materials, the process of gelification, that can be physical (based on physical interactions) and/or chemical (based on covalent crosslinking), has to be carried out. In this work we used dynamic light scattering (DLS) and rheometry to monitor the covalent gelification of chitosan solutions by glutaraldehyde. Intensity correlation function (ICF) data was obtained from DLS and the exponential stretched Kohrausch-William-Watts function (KWW) was fitted to them. The parameters of the KWW equation, &#946;, &#915; and C were evaluated. These methods were effective in clarifying the process of sol-gel transition, with the emergence of non-ergodicity, and determining the range of gelation observed in about 10-20 minutes. The dependence between apparent viscosity on reaction time was used to support the discussion proposed. / G?is s?o materiais que possuem aplica??es em v?rias ?reas, tais quais, na ind?stria de tintas, alimentos e farmac?utica. Os m?todos empregados para obten??o dos g?is podem ser f?sicos (intera??es f?sicas) e/ou qu?micos (baseado em intera??es covalentes), tal processo, ? denominado gelifica??o. Neste trabalho, o processo de gelifica??o de quitosana/glutaralde?do foi monitorado utilizando reometria e espalhamento da luz (DLS). As fun??es de correla??o de intensidade (ICF) foram obtidas atrav?s de DLS e a equa??o de Kohrausch-William-Watts (KWW) foi ajustada com os dados experimentais. Os par?metros da equa??o KWW, &#946;, &#915; e C foram avaliados. Estes m?todos foram eficazes na clarifica??o do processo que compreende a transi??o sol-gel, com o surgimento da n?o-ergodicidade, e na determina??o da faixa de gelifica??o, observada em torno de 10-20 minutos. A depend?ncia da viscosidade aparente em fun??o do tempo foi utilizada para comprovar o tempo de gelifica??o observado no DLS.

Particle analysis using multiwavelength UV-visible spectroscopy provides the potential for extracting quantitative red blood cell information, such as hemoglobin concentration, cell size, and cell count. However, if there is a significant presence of hypochromism as a result of the concentrated hemoglobin (physiological value of 33%), successful quantification of red cell values would require a correction. Hypochromism has been traditionally defined as a decrease in absorption relative to the values expected from the Beer-Lambert Law due to electronic interactions of chromophores residing in close proximity of one another. This phenomenon has been suggested to be present in macroscopic systems composed of strong chromophores such as nucleic acids, chlorophyll, and hemoglobin. The study presented in this dissertation examines the presence of hypochromism in red blood cells as a part of a larger goal to qualitatively and quantatively characterize red blood cells using multiwavelength UV-visible spectroscopy. The strategy of the study was three-fold: 1) to determine the instrumental configuration that would provide the most complete information in the acquired spectra, 2) to develop an experimental model system in which the hemoglobin content in red blood cells could be modified to various concentrations, and 3) to implement an interpretation model based on light scattering theory (which accounts for both the scattering and absorption components of the optical density spectrum) to provide quantitative information for the experimental system. By this process, hypochromicity was redefined into two categories with molecular hypochromicity representing the traditional definition and macroscopic hypochromicity being an attenuation of the absorption component due to a scattering-related effect. Successful simulations of experimental red cell spectra containing various amounts of hemoglobin were obtained using the theoretical model. Furthermore, successful quantitative interpretation of the red blood cell spectra was achieved in the context of corpuscular hemoglobin concentration, corpuscular volume, and cell count solely by accounting for the scattering and absorption effects of the particle, indicating that molecular hypochromicity was insignificant in this macroscopic system.

<p>The properties of Mercury's regolith have been investigated at optical and near-infrared wavelengths with high-resolution imaging, photometric, and spectroscopic observations with the Swedish Vacuum Solar Telescope and the Nordic Optical Telescope. </p><p>A new global optical map at a spatial resolution of 200 km shows that the well known (from Mariner 10) and poorly known hemispheres are indistinguishable with respect to the distribution, number density, and morphological parameters of bright albedo features. This indicates a globally uniform recent (<3 Gyr) geologic evolution, a compositionally very homogeneous surface and the absence of a lunar-like mare–terrae albedo dichotomy.</p><p>It is found that the spectrum of Mercury is linear, strongly sloped, lacks detectable absorption features and displays a unique relation between the continuum slope and photometric geometry. Mercury has a photometrically smoother surface than the average near-side Moon, and is 10–15% fainter and 50% more back scattering in the V-band. Unlike the case for the Moon, the average single-particle backscattering anisotropy increases with wavelength.</p><p>Intimate regolith mixing models are used to determine a probable surface composition of predominantly Ca-rich labradorite plagioclase feldspar with minor low-iron enstatitic orthopyroxene, and rule out high-iron pyroxenes or olivines as other than insignificant constituents. Abundances of FeO ~1.2 wt%, TiO₂ ~0 wt%, and submicroscopic metallic iron ~0.1–0.3 wt% are found for the average surface. This implies an optically active grain size of 15–30 μm that is a factor of two smaller than for the Moon.</p><p>A numerical integration study shows that hermeocentric orbits with semi-major axes <30 mercurian radii for elliptic retrograde, and circular prograde, object are stable for durations in excess of 4.5 Myr. The weak gravitational scattering effect of Mercury indicates that re-impacting particles may have been important for the early evolution of its crust.</p>

<p>Comets are the most primordial and least evolved bodies in the Solar System. As such, they are unique sources of information regarding the early history of the Solar System. However, little is known about cometary nuclei since they are very difficult to observe due to the obscuring coma. Indirect methods are therefore often used to extract knowledge about nucleus parameters such as size, shape, density, material strength, and rotational properties. For example, tidal and non-tidal splitting of cometary nuclei can provide important information about nuclear densities and material strengths, but only if the criteria for mechanical stability are well known. Masses and densities of cometary nuclei can also be obtained by studying orbital modifications due to non-gravitational forces, but only if the thermophysics of comets can be modelled accurately. </p><p>A detailed investigation is made regarding the mechanical stability of small Solar System bodies. New expressions for the Roche distance are derived, as functions of the size, shape, density, material strength, rotational period, and spin axis orientation of a body. The critical rotational period for centrifugal breakup in free space is also considered, and the resulting formulae are applied to comets for which the size, shape and rotational period have been estimated observationally, in order to place constraints on their densities and material strengths. </p><p>A new thermophysical model of cometary nuclei is developed, focusing on two rarely studied features - layer absorption of solar energy, and parallel modelling of the nucleus and innermost coma. Sophisticated modelling of radiative transfer processes and the kinetics of gas in thermodynamic non-equilibrium form the basis for this work. The new model is applied to Comet 19P/Borrelly, and its density is estimated by reproducing the non-gravitational changes of its orbit.</p>