Parmi les nanoparticules aptes à accompagner la radiothérapie en clinique, les nanoparticules à base d’oxyde de gadolinium paraissent pertinentes, de part leur multimodalité en imagerie et leur effet radiosensibilisant prouvé in vitro et in vivo. Cet effet de radiosensibilisation est exceptionnel notamment sur des cellules cancéreuses radiorésistantes de la lignée SQ20B (carcinome squameux tête et cou) et uniquement pour des doses modérées de nanoparticules (aux alentours de 0.6 mM en Gd). Les clichés de microscopie électronique ont montré que ce maximum de radiosensibilisation est dû à une internalisation maximale des particules dans le cytoplasme, notamment par macropinocytose. Ce mécanisme d’internalisation est caractérisé par la formation de vésicules de grandes tailles, ou macropinosomes. Il se produit suivant deux étapes : la formation d’agglomérats de nanoparticules à proximité de la membrane cellulaire puis la récupération de ceux-ci par les lamellipodes de la cellule. La première étape est fortement dépendante des caractéristiques physicochimiques des particules, plus particulièrement leur potentiel zêta qui détermine la taille de l’agglomérat, et de la distance les séparant de la cellule. Dans des gammes de taille et de distance à la membrane optimales aux concentrations modérées, l’agglomérat peut être récupéré par les lamellipodes de la cellule. Il s’en suit une protubérance sur la membrane plasmique formant un macropinosome contenant les agglomérats de nanoparticules. Cet endosome précoce suivra ensuite le schéma d’endocytose classique dans le cytoplasme en fusionnant avec des corps multivésiculaires, uniquement visible en microscopie électronique à transmission, pouvant contenir des enzymes de dégradation détruisant leur contenu. Ces enzymes rendent le pH acide à l’intérieur de la vésicule. Plus les nanoparticules sont proches du noyau cellulaire plus leur effet radiosensibilisant sera efficace. Les espèces oxygénées réactives (ROS) et les électrons Auger et secondaires peuvent atteindre l’ADN du noyau plus facilement. A faibles doses (<0.4 mM) très peu de nanoparticules sont internalisées et un effet linéaire de la radiosensibilisation est observé jusqu'à 0.6 mM. A fortes doses (> 0.7 mM) les nanoparticules forment une couronne autour de la membrane cellulaire agissant comme écran, empêchant ainsi les ROS et les électrons générés de pouvoir atteindre l’ADN et induire des cassures, le noyau étant situé à quelques micromètres de la membrane cellulaire. Les résultats obtenus ouvrent la voie sur la nécessité de contrôler l'internalisation cellulaire des nanoparticules en contrôlant leur chimie, laissant envisager ainsi des opportunités prometteuses dans le domaine de la radiothérapie assistée par nanoparticules délivrant de faibles doses de radiation aux patients. / Over the last few decades, nanoparticles have been studied in theranostic field with the objective of exhibiting a long circulation time through the body coupled to major accumulation in tumor tissues, rapid elimination, therapeutic potential and contrast properties. In this context, we developed sub-5 nm gadolinium-based nanoparticles that possess in vitro efficient radiosensitizing effects at moderate concentration when incubated with head and neck squamous cell carcinoma cells (SQ20B). Two main cellular internalization mechanisms were evidenced and quantified: passive diffusion and macro- pinocytosis. Whereas the amount of particles internalized by passive diffusion is not sufficient to induce in vitro a significant radiosensitizing effect, the cellular uptake by macropinocytosis leads to a successful radiotherapy in a limited range of particles incubation concentration. Macropinocytosis processes in two steps: formation of agglomerates at vicinity of the cell followed by their collect via the lamellipodia (i.e. the “arms”) of the cell. The first step is strongly dependent on the physicochemical characteristics of the particles, especially their zeta potential that determines the size of the agglomerates and their distance from the cell. These results should permit to control the quantity of particles internalized in the cell cytoplasm, promising ambitious opportunities towards a particle-assisted radiotherapy using lower radiation doses.

Ce travail a porté sur la caractérisation et la quantification en 3D de la répartition de charges de différents types (nanoparticules, nanotubes, etc.) dans des matrices polymères. Nous nous focalisons sur les techniques de tomographie en microscopie électronique. Une approche multiple en tomographie électronique a été réalisée : la tomographie en FIB/MEB (faisceau d’ions focalisé/microscope électronique à balayage), la tomographie en MEB et la tomographie en MET (microscope électronique en transmission). Les nanocomposites polymère sont généralement élaborés aux fins d’améliorer les propriétés physiques (mécanique, électrique, etc.) du matériau polymère constituant la matrice, grâce à une addition contrôlée de charges nanométriques. La caractérisation de tels matériaux, et l’établissement de corrélations précises entre la microstructure et les propriétés d’usage, requièrent une approche tri-dimensionnelle. En raison de la taille nanométrique des charges, la microscopie électronique est incontournable. Deux systèmes de nanocomposite polymère ont été étudiés par une approche multiple de tomographie électronique : P(BuA-stat-S)/MWNTs (copolymère statistique poly (styrène-co-acrylate de butyl) renforcé par des nanotubes de carbone multi-parois), et P(BuA-stat-MMA)/SiO2 (copolymère statistique poly(butyl acrylate-co-methyl methacrylate) renforcé par des nanoparticules de silice). Par combinaison de divers techniques, la caractérisation et la quantification des nanocharges ont été possibles. En particulier, la taille, la fraction volumique et la distribution des charges ont été mesurées. Cette étude a ainsi fourni des informations en 3D qui contribuent à mieux comprendre les propriétés des nanocomposites. Une attention particulière a été portée aux artefacts et causes d’erreur possibles durant l’étape de traitement 3D. Nous avons également essayé de comparer les différentes techniques utilisées du point de vue de leurs avantages et inconvénients respectifs, en dégageant des possibilités d’amélioration future. / This work is focused on the characterization and quantification of the 3D distribution of different types of fillers (nanoparticles, nanotubes, etc.) in polymer matrices. We have essentially used tomography techniques in electron microscopy. Multiple approaches to electron tomography were performed: FIB-SEM (focused ion beam/scanning electron microscope) tomography, SEM tomography and TEM (transmission electron microscope) tomography. Polymer nanocomposites are basically synthesized in order to improve the physical properties (mechanical, electric, etc.) of the pure polymer constituting the matrix, by a controlled addition of fillers at the nanoscale. The characterization of such materials and the establishment of accurate correlations between the microstructure and the modified properties require a three-dimensional approach. According to the nanometric size of the fillers, electron microscopy techniques are needed. Two systems of polymer nanocomposites have been studied by multiple electron tomography approaches: P(BuA-stat-S)/MWNTs (statistical copolymer poly(styrene-co-butyl acrylate) reinforced by multi-walled carbon nanotubes) and P(BuA-stat-MMA)/SiO2 (statistical copolymer poly(butyl acrylate-co-methyl methacrylate) reinforced by silica nanoparticles). By combining various techniques, the characterization and the quantification of nanofillers were possible. In particular, statistics about size, distribution and volume fraction of the fillers were measured. This study has then provided 3D information, which contributes to a better understanding of properties of the nanocomposites. Attention has been paid to analyze carefully original data, and artifacts and causes of errors or inaccuracy were considered in the 3D treatments. We also attempted to compare benefits and drawbacks of all techniques employed in this study, and perspectives for future improvements have been proposed.

Despite increasing concern about the presence of heavy metals, pesticides and other toxins in indoor environments, very little is known about the physical and chemical composition of ordinary household dust. This study represents the first systematic investigation of the mineralogical composition of indoor dust in residential housing in Canada. Specimens of dust were obtained from homes in six geographically separate cities in the Province of Ontario: two located on the metamorphic and igneous rocks of the Precambrian Canadian Shield (Thunder Bay and Sudbury), the other four located on Palaeozoic limestone and shale dominated bedrock (Barrie, Burlington, Cambridge, and Hamilton). Forty samples of household vacuum dust were obtained. The coarse fraction (80 – 300 µm) of this dust was subjected to flotation (using water) to separate the organic components (e.g. insect fragments, dander), natural and synthetic materials (e.g. fibres, plastics) from the mineral residue. The mineral fraction was then analyzed using quantitative point counting, polarizing light microscopy, powder X-ray diffraction and scanning electron microscopy methods. Despite the great distances between the sampling localities and the distinct differences in bedrock geology, the mineral fraction of dust from all six cities is remarkably similar and dominated by quartz and feldspar, followed by lithic fragments, calcite, and amphibole. Some evidence of the influence of local geology can nevertheless be found. For example, a relatively higher proportion of sulphide minerals is observed in the two cities on the Canadian Shield where these minerals are clearly more abundant in the bedrock. Specimens from Sudbury, Canada’s largest mining centre located atop a nickel-sulphide mineral deposit, showed the highest sulphide contents. Quartz is the dominant mineral in all cities. All quartz grains have internal strain features and fluid inclusions that are indicative of a metamorphic-igneous provenance. In all cities, sand is used on the streets as an abrasive for traction during the icy winter season. This sand is obtained in all cases from local glaciofluvial deposits that were ultimately derived principally from the rocks of the Canadian Shield in the last Pleistocene glaciations that affected all of Ontario. Thus, tracking in sand is the most plausible mechanism by which quartz was introduced into these homes since sampling was done, in all cases, in the winter season. The results indicate that glacial deposits dominate the mineral composition of indoor dust in Ontario cities and that nature of the bedrock immediately underlying the sampling sites is relatively of minor importance.

The goals of this research project were to identify the various insects observed to visit inflorescences of Echinacea angustifolia DC, and to rank these visitors according to their importance as pollinators of E. angustifolia in Saskatchewan. Studying nectar and the nectary is essential to understanding the interaction of disc florets with pollinators. Nectar-sugar production by disc florets of E. angustifolia and E. purpurea (L. Moench) was quantified from anthesis to cessation with production per disc floret peaking in the afternoon of the staminate phase (191.7 µg) and at midday of the first day of the pistillate phase (156.6 µg), respectively. Morphology of the disc-like floral nectaries of both Echinacea species was studied, as well as the ultrastructure of the nectary of E. purpurea. Modified stomata on the nectary rim are the most likely exits for nectar, but creases in the epidermis may also participate. The nectary of E. purpurea is vascularized by phloem alone, which occurred adjacent to the epidermis. Companion cells possessed wall ingrowths, and these cells may unload arriving sugar destined for either an apoplastic or symplastic pathway. Lobed nuclei were a key feature of secretory parenchyma cells, as was a predominance of mitochondria, suggesting that energy-requiring eccrine secretion predominates in E. purpurea. E. angustifolia exhibited a generalist pollination system, with pollinating insects belonging to the orders Coleoptera, Diptera, Hymenoptera, and Lepidoptera. The pollination efficiency of visitors was determined by single insect visits to bagged, virgin inflorescences followed by quantifying pollen tubes at the bases of receptive styles and/or calculating the percentage of shrivelled styles. It was determined that bumble bees (Bombus spp.) were efficient pollinators, indicating that they would likely contribute much to the pollination of E. angustifolia. Grasshopper bee flies (Systoechus vulgaris Loew) were plentiful but individually were not efficient pollinators, but taken together, they provided much pollination. Golden blister beetles (Epicauta ferruginea Say) were efficient pollinators but where yellow-petalled flowers occurred, their numbers on E. angustifolia decreased. Honey bees (Apis mellifera L.) were efficient pollinators and were present in low numbers without managed introduction. Pierid (2003) butterflies were regular visitors and efficient pollinators, and likely contributed significantly to E. angustifolia pollination. When introduced, the alfalfa leafcutter bee (Megachile rotundata Fabr.) preferred not to forage on E. angustifolia and as such, these solitary bees were not suitable as managed pollinators. In large agricultural plantings of E. angustifolia, however, native insects may not be capable of providing sufficient pollination for seed production when floral competition occurs.

Despite increasing concern about the presence of heavy metals, pesticides and other toxins in indoor environments, very little is known about the physical and chemical composition of ordinary household dust. This study represents the first systematic investigation of the mineralogical composition of indoor dust in residential housing in Canada. Specimens of dust were obtained from homes in six geographically separate cities in the Province of Ontario: two located on the metamorphic and igneous rocks of the Precambrian Canadian Shield (Thunder Bay and Sudbury), the other four located on Palaeozoic limestone and shale dominated bedrock (Barrie, Burlington, Cambridge, and Hamilton). Forty samples of household vacuum dust were obtained. The coarse fraction (80 – 300 µm) of this dust was subjected to flotation (using water) to separate the organic components (e.g. insect fragments, dander), natural and synthetic materials (e.g. fibres, plastics) from the mineral residue. The mineral fraction was then analyzed using quantitative point counting, polarizing light microscopy, powder X-ray diffraction and scanning electron microscopy methods. Despite the great distances between the sampling localities and the distinct differences in bedrock geology, the mineral fraction of dust from all six cities is remarkably similar and dominated by quartz and feldspar, followed by lithic fragments, calcite, and amphibole. Some evidence of the influence of local geology can nevertheless be found. For example, a relatively higher proportion of sulphide minerals is observed in the two cities on the Canadian Shield where these minerals are clearly more abundant in the bedrock. Specimens from Sudbury, Canada’s largest mining centre located atop a nickel-sulphide mineral deposit, showed the highest sulphide contents. Quartz is the dominant mineral in all cities. All quartz grains have internal strain features and fluid inclusions that are indicative of a metamorphic-igneous provenance. In all cities, sand is used on the streets as an abrasive for traction during the icy winter season. This sand is obtained in all cases from local glaciofluvial deposits that were ultimately derived principally from the rocks of the Canadian Shield in the last Pleistocene glaciations that affected all of Ontario. Thus, tracking in sand is the most plausible mechanism by which quartz was introduced into these homes since sampling was done, in all cases, in the winter season. The results indicate that glacial deposits dominate the mineral composition of indoor dust in Ontario cities and that nature of the bedrock immediately underlying the sampling sites is relatively of minor importance.

Gegenstand dieser Arbeit ist die Herstellung nicht hierarchischer und hierarchischer, poröser Polymermembranen mittels eines Templatverfahrens. Bei der Herstellung der hierarchischen Membranen wird eine Stützschicht mit mikrometergroßen Mulden und eine aktive Membranschicht mit submikrometergroßen Poren in einem Arbeitsschritt und aus einem Material erzeugt. Als Template für die Poren der nicht hierarchischen Membranen bzw. Mulden der hierarchischen Membran in der Stützschicht dienen Flüssigkeitstropfen. Diese werden auf Substraten mit Bereichen unterschiedlicher Benetzbarkeit erzeugt. Die Substrate werden anschließend mit einer Polymerlösung überschichtet, welche im Falle der hierarchischen Membranen sphärische, monodisperse Siliziumdioxidpartikel enthält. Die Siliziumdioxidpartikel ordnen sich bevorzugt in der Grenzfläche zwischen den Templattropfen und der Polymerlösung an. Nach Verdunsten des Lösungsmittels, Entfernen des Substrats und ggf. der Siliziumdioxidpartikel werden poröse Polymermembranen erhalten. Die nicht hierarchischen weisen Poren in der Größe der Templattropfen aus. Die hierarchischen Membranen zeigen dagegen eine Stützstruktur mit mikrometergroßen Mulden, entstanden durch die Templattropfen und eine Schicht auf der Oberseite der Membran mit submikrometergroßen Poren, die durch die Siliziumdioxidpartikel gebildet wurden. Außerdem wird gezeigt, wie das dargelegte Verfahren auf die Herstellung von Membranen aus dem Monomer VISIOMER HEMA-TMDI übertragen werden konnte

The preparation of polymeric hybrid composite consisting of organic and inorganic fillers is of interest for industries like automotive, construction and packaging. In order to understand and predict the physical and chemical properties of these hybrid composites, it is necessary to fully understand the nature and properties of the employed fillers. In this study, the preparation of polypropylene hybrid composite consisting of wheat straw and clay was investigated. A detailed study was performed on wheat straw from South Western Ontario region. The effect of grinding the straw and compounding it with polypropylene was investigated. Experiments were carried out to identify the thermal stability of the ground wheat straw with respect to their size and composition. It was important to identify a correlation between these properties in order to minimize the straw degradation by processing and also to improve the final properties of the hybrid composite. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. Sample test bars were prepared by injection moulding. The composition of the constituents of the hybrid composite; percentages of wheat straw, clay and coupling agent, were varied in order to investigate their influence on thermal stability, water resistance and mechanical properties. The results of the study indicated that grinding the wheat straw with a hammer mill produced particles with different sizes and shapes. It was found that through the grinding system all particles, regardless of their size, had a multi-layered structure similar to the plant structure. Further hammer milling did not produce plant particles with long aspect ratios that would be expected in a defibrillation process. Analysis of the chemical composition of wheat straw particles of different sizes and shapes was used to measure the ratio of hemicelluloses: lignin and the ash content. It was found that the large particles contained more amount of lignin whereas smaller particles had larger amount of ash content. The thermal stability of the particles was found to be a function of particle size rather than the lignin content. Particle size analysis on the wheat straw particles after the extrusion process indicated a reduction in the particle length and aspect ratio. The thermal stability of the composites was found to be enhanced by the addition of clay particles at higher temperature and the addition of coupling agent at lower temperatures. Increasing the amount of wheat straw and clay content increased the flexural modulus and reduced the resistance for water absorption. Increasing the amount of coupling agent also increased the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscopy revealed that coupling agent increased the interfacial interaction between the particles and the polymer matrix.

The preparation of polymeric hybrid composite consisting of organic and inorganic fillers is of interest for industries like automotive, construction and packaging. In order to understand and predict the physical and chemical properties of these hybrid composites, it is necessary to fully understand the nature and properties of the employed fillers. In this study, the preparation of polypropylene hybrid composite consisting of wheat straw and clay was investigated. A detailed study was performed on wheat straw from South Western Ontario region. The effect of grinding the straw and compounding it with polypropylene was investigated. Experiments were carried out to identify the thermal stability of the ground wheat straw with respect to their size and composition. It was important to identify a correlation between these properties in order to minimize the straw degradation by processing and also to improve the final properties of the hybrid composite. The composite samples were prepared through melt blending method using a co-rotating twin-screw extruder. Sample test bars were prepared by injection moulding. The composition of the constituents of the hybrid composite; percentages of wheat straw, clay and coupling agent, were varied in order to investigate their influence on thermal stability, water resistance and mechanical properties. The results of the study indicated that grinding the wheat straw with a hammer mill produced particles with different sizes and shapes. It was found that through the grinding system all particles, regardless of their size, had a multi-layered structure similar to the plant structure. Further hammer milling did not produce plant particles with long aspect ratios that would be expected in a defibrillation process. Analysis of the chemical composition of wheat straw particles of different sizes and shapes was used to measure the ratio of hemicelluloses: lignin and the ash content. It was found that the large particles contained more amount of lignin whereas smaller particles had larger amount of ash content. The thermal stability of the particles was found to be a function of particle size rather than the lignin content. Particle size analysis on the wheat straw particles after the extrusion process indicated a reduction in the particle length and aspect ratio. The thermal stability of the composites was found to be enhanced by the addition of clay particles at higher temperature and the addition of coupling agent at lower temperatures. Increasing the amount of wheat straw and clay content increased the flexural modulus and reduced the resistance for water absorption. Increasing the amount of coupling agent also increased the flexural modulus and resistance for water absorption. The morphological study by scanning electron microscopy revealed that coupling agent increased the interfacial interaction between the particles and the polymer matrix.

The goals of this research project were to identify the various insects observed to visit inflorescences of Echinacea angustifolia DC, and to rank these visitors according to their importance as pollinators of E. angustifolia in Saskatchewan. Studying nectar and the nectary is essential to understanding the interaction of disc florets with pollinators. Nectar-sugar production by disc florets of E. angustifolia and E. purpurea (L. Moench) was quantified from anthesis to cessation with production per disc floret peaking in the afternoon of the staminate phase (191.7 µg) and at midday of the first day of the pistillate phase (156.6 µg), respectively. Morphology of the disc-like floral nectaries of both Echinacea species was studied, as well as the ultrastructure of the nectary of E. purpurea. Modified stomata on the nectary rim are the most likely exits for nectar, but creases in the epidermis may also participate. The nectary of E. purpurea is vascularized by phloem alone, which occurred adjacent to the epidermis. Companion cells possessed wall ingrowths, and these cells may unload arriving sugar destined for either an apoplastic or symplastic pathway. Lobed nuclei were a key feature of secretory parenchyma cells, as was a predominance of mitochondria, suggesting that energy-requiring eccrine secretion predominates in E. purpurea. E. angustifolia exhibited a generalist pollination system, with pollinating insects belonging to the orders Coleoptera, Diptera, Hymenoptera, and Lepidoptera. The pollination efficiency of visitors was determined by single insect visits to bagged, virgin inflorescences followed by quantifying pollen tubes at the bases of receptive styles and/or calculating the percentage of shrivelled styles. It was determined that bumble bees (Bombus spp.) were efficient pollinators, indicating that they would likely contribute much to the pollination of E. angustifolia. Grasshopper bee flies (Systoechus vulgaris Loew) were plentiful but individually were not efficient pollinators, but taken together, they provided much pollination. Golden blister beetles (Epicauta ferruginea Say) were efficient pollinators but where yellow-petalled flowers occurred, their numbers on E. angustifolia decreased. Honey bees (Apis mellifera L.) were efficient pollinators and were present in low numbers without managed introduction. Pierid (2003) butterflies were regular visitors and efficient pollinators, and likely contributed significantly to E. angustifolia pollination. When introduced, the alfalfa leafcutter bee (Megachile rotundata Fabr.) preferred not to forage on E. angustifolia and as such, these solitary bees were not suitable as managed pollinators. In large agricultural plantings of E. angustifolia, however, native insects may not be capable of providing sufficient pollination for seed production when floral competition occurs.

Numerous organisms produce ornately detailed inorganic structures (often known as shells) with features on length scales from 50 nm to several centimeters. One class of such organisms are the diatoms; microscopic algae that form silica frustules. Another group of algae, the coccolithophorids, produce similar calcium carbonate structures. Over 100,000 species comprise these two classes of algae, every one of which is endowed with a unique cytoskeleton structure. Using various types of displacement reactions, the chemistry of the original structure can be modified to produce a new material. Magnesium vapor has been found to displace the silicon in diatom frustules to yield an MgO structure. The conversion has been reported at temperatures from 650°C to 900°C. In the current work, the conversion and processing of silica frustules to MgO was examined in depth. The effect of reaction temperature on grain size and extent of conversion was evaluated. With the goal of obtaining high purity MgO structures, various methods for removing the silicon products of reaction were investigated. Wet chemistry and high temperature vapor etches were evaluated. The MgO reaction served as an intermediate step in the production of magnesium tungstate diatoms, which were imbued with photoluminescent properties. Reactions were identified to allow the conversion of calcium carbonate (calcite) structures to alternative chemistries. Calcite sand-dollars were converted to calcium tungstate or calcium molybdate by aqueous solution chemistry. In this process, sand dollar tests (shells) and coccolithophore frustules were reacted with ammonium para-molybdate or ammonium para-tungstate. The reactions were evaluated for shape preservation, phase purity, and photoluminescence of the structures.