Nanotechnology as a science is emerging rapidly. As materials are synthesized and utilized at the nanometer size scale, concerns of potential health and safety effects are arising. In an effort to elucidate the physicochemical characteristics of nanoparticles influential in toxicological studies, surface properties of metal oxide and carbonaceous nanoparticles were measured. These properties include zeta potential, dissolution and surface-bound chemical components. Subsequently, the role of these properties in oxidative stress was examined in vitro. This work identifies the influence that pH has on the zeta potential of nanoparticles. The zeta potential has the ability to alter colloidal stability, as the largest nanoparticle agglomerate is seen at or near the isoelectric point for each of the particles tested. Furthermore, it was observed that metal oxide nanoparticles which exhibit a charged surface at physiological pH, lead to decreased in vitro cellular viability as compared to those that were neutral. Thus, nanoparticle zeta potential may be an important factor to consider when attempting to predict nanoparticle toxicity. Real world exposure to nanoparticles is a mixture of various particulates and organics. Therefore, to simulate this particle mixture, iron oxide (Fe2O3) and engineered carbon black (ECB) were utilized in combination to identify potential synergistic reactions. Following in vitro exposure, both nanoparticle types are internalized into endosomes, where liberated Fe3+ reacts with hydroquinone moieties on the ECB surface yielding Fe2+. This bioavailable iron may then generate oxidative stress through intracellular pathways including the Fenton reaction. As oxidative stress is common in particulate toxicology, a comparison between the antioxidant defenses of epithelial (A549) and mesothelial (MeT-5A) cell lines was made. The A549 cell line exhibits alterations in the NRF2-KEAP1 transcription factor system and therefore retains high basal levels of phase II antioxidants. Both cell types were exposed to 33 nm silica where intracellular oxidant generation coupled with markers of oxidative stress were observed. While the MeT-5A cells exhibited a decrease in cell viability, the A549 cell line did not. Therefore, proper characterization of both material and biological systems prior to toxicity testing will help to further define the risks associated with the use of nanotechnology.

Polymeric nano and microparticles are important tools for an increasing variety of applications in the life sciences such as cellular delivery, sensing and imaging, with a fundamental requirement being particle functionalisation. Herein, the use of zeta potential measurements is described as a convenient tool to allow a variety of chemical reactions to be rapidly monitored on particles. To allow multifunctionalisations these particles need to be orthogonally modified. As part of this thesis, novel dual-functionalised aminomethyl and boronic acid particles were synthesised. These particles could be modified via amide formation and palladiummediated cross coupling, with applications demonstrated in cellular delivery and cellbased cargo release. The requirement for bright fluorescent particles for applications in the life sciences was addressed by the synthesis and analysis of particles prepared using polymerisable fluorescein derivatives. Although nanoparticles are a promising technology to solve a variety of problems, their behaviour in biological systems is not fully understood. Herein, the effects of the particle’s surface chemistry on cellular uptake and toxicity were investigated.

Thesis (M.S.)--Oregon State University, 2009. / Printout. Includes bibliographical references (leaves 34-38). Also available on the World Wide Web.

Thesis (M.S.)--Duquesne University, 2009. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. 82-90) and index.

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<p> In this study the experiments were designed to measure the geochemical and surface charge (zeta potential) changes with time for two crushed samples of feldspar (Na-fs and K-fs) over the pH range of most natural waters (5 to 9). These experiments show: </p> <p> (a) the importance of adsorption/desorption phenomena in both short-term and long-term feldspar dissolution, and probably for chemical weathering in general; </p> <p> (b) that the generalized curve which characterizes the geochemical data (an initial rapid rise to a peak followed by a decrease to a lower, either constant or later increasing value) is consistent with a consideration of the adsorption/desorption process (i.e., the formation of the double layer) taking place at the feldspar surface and with the simple dissolution of the mineral; </p> <p> (c) that the cation-silica ratios (Na₂O/SiO₂, K₂O/SiO₂, CaO/SiO₂) of the solution compared to those in the original feldspar indicate an initially incongruent dissolution which tends towards congruency during the latter part of the experiments. </p> <p> From information in the Iiterature and the results of these experiments. it may be concluded that: </p> <p> (a) the most important or master variables in chemical weathering are abrasion, minerologic or crystallographic factors such as twinning, exsolution regions, impurities, fractures and grain size, and solution composition and concentration. pH does not appear to be a master variable in most natural waters, especially for long-term weathering, and the chemical composition of the mineral phase is also not a good criterion for predicting weathering behaviour; and </p> <p> (b) the most extreme chemical weathering should occur in a high energy environment, either for physical reasons (i.e., high abrasion due to extreme relief) or for chemical reasons (i.e., high rainfall). </p> / Thesis / Master of Science (MSc)

In light of increased stream temperatures due to urbanization and climate change, the<br />effect of water temperature on cohesive soil erosion should be explored. The objectives of this study are to: determine the effect of water temperature on the erosion rates of clay; determine how erosion rates vary with clay mineralogy; and, explore the relationship between zeta potential and erosion rate. Samples of kaolinite- and montmorillonite-sand mixtures, and vermiculite-dominated soil were placed in the wall of a recirculating flume channel using a vertical sample orientation. Erosion rate was measured under a range of shear stresses (0.1-20 Pa) for a period of five minutes per shear stress at water temperatures of 12, 20, and 27�"C. The zeta potential was determined for each clay type at the three testing temperatures and compared to mean erosion rates. The kaolinite erosion rate doubled when the temperature increased from 12 to 20�"C, and erosion of vermiculite samples tripled when the temperature increased from 20 to 27�"C. The montmorillonite samples generally eroded through mechanical failure rather than fluvial erosion, and the limited fluvial erosion of the montmorillonite-sand mixture was not correlated with water temperature. The data suggest correlation between zeta potential and erosion rate; however, due to the small sample size (n=3), statistically significant correlation was not indicated. Research should continue to explore the influence of water temperature on cohesive soil erosion to better understand the influence of clay mineralogy. Due to the high degree of variability in cohesive soil erosion, multiple replications should be used in future work. The vertical sample orientation enabled discrimination between fluvial erosion and mass wasting and is recommended for future studies. / Master of Science

I detta projekt har experiment utförts med mål att förse kommunalförbundet Norrvatten med data som kan användas som underlag för beslutsfattande angående om deras fällningslinjer i vattenreningsprocessen ska köras i flotation eller sedimentering. För detta ändamål har koncentrationen av poly- och perfluorerade alkylsubstanser (PFAS) samt karaktär av agglomererade partiklar (flockar) undersökts och jämförts mellan fällningslinjer som körs i olika konfigurationer. För flockkaraktär har skapandet och stabiliteten av flockar varit av intresse, eftersom flotation har ett mer turbulent flöde där flockarna riskerar att brista. Partikelstorlek, storleksfördelning och zeta potential identifierades som egenskaper som reflekterar flockarnas karaktär, dessa analyserades i en zetasizer. Koncentrationen av elva vanligt förekommande PFAS ämnen analyserades i projektet. Resultatet av flockkaraktär tyder på att det ej fanns någon större skillnad i skapandet av flockar samt deras stabilitet mellan de olika fällningslinjerna som undersökts. Detta eftersom zeta potentialen var identisk (-6.45 mV) för de analyserade proverna från respektive process. Analyserna och provberedningen bedömdes ha en hög mätosäkerhet, och några förbättringar som föreslås för att öka säkerheten är genomförande av komplementerande fotoanalys för att bekräfta likheter i utseende mellan flockar, samt att genomföra mer analyser så att en statistisk giltighet av analysen kan kvantifieras. För PFAS koncentrationen så var koncentrationen av PFAS lägre i utgående vatten från fällningslinje som körs i sedimentation (7.5 ng/l), jämfört med prov från linje som körs i flotation (9.2 ng/l). För fällningslinjen som kördes i flotation så skapades skum med höga koncentrationer av PFAS (3800 ng/l) jämfört med analyserade vattenprover (5.5–9.2 ng/l), detta identifierades som en potentiell källa för PFAS-avlägsning. Resultaten av PFAS baserades endast på en provtagningsserie, och förbättringar av validitet kan åstadkommas genom samling av mer analysdata för samma processer, och genom att analysera ett av proverna i två olika instrument, som båda analyserar PFAS koncentration. / In this project, attempts have been made to collect data that allows the municipal association Norrvatten in the decision-making process on the  flotation/ sedimentation step of their water treatment process. In this sense, poly- and perfluorinated alkyl substances (PFAS) concentration and the characteristics of agglomerated particles (flocs) have been investigated and compared between the two modes that the process can be operated. For the floc characteristics, the creation and stability of the flocs were investigated, and the particle size, size distribution and zeta potential was identified as important properties and thereafter analysed using the instrument zetasizer. The concentration of eleven different PFAS compounds were analysed. The results of floc characteristics show that there is no major difference in creation and breakage of flocs in the two investigated modes, since the analysed samples had the same zeta potential, -6.45 mV. The results were deemed uncertain because of varying results, and improvement suggestions include using photoanalysis to confirm similar floc appearances and to produce more data so a statistical validity can be quantified. As for the PFAS concentration, the concentration of PFAS were slightly lower in the treatment step in which sedimentation was utilized (7.5 ng/l) compared to when flotation was utilized (9.2 ng/l). The flotation mode did, however, create foam with a high PFAS concentration (3800 ng/l) compared to the liquid samples (5.5-9.2 ng/l), so a potential PFAS removal source was identified. The results were based on one sample series, so improvements of validity can be achieved by gathering more data, analysing more samples, and analysing the same sample in two different instruments measuring PFAS concentrations.

High capacitance devices were developed using rapid electrophoretic deposition (EPD) of barium titanate (BaTiO3) on ultrasonically etched nickel (Ni) substrates. The microstructural and electrical properties of films with varying thicknesses, sintering temperatures and substrate etching times were investigated to study their effect on the capacitance. Although increasing the capacitance was the primary goal, decreasing manufacturing costs and reducing environmental impact was also considered. After confirming the tetragonality and particle size of a 0.2 µm hydrothermal powder, it was dispersed in an aqueous-organic mixture of ethanol, acetone and water. A zeta potential of 50 mV was observed at the EPD pH level (6.8). Flocculation or coagulation was not likely in this situation. Therefore, mixing water with an organic solution was an effective method for reducing environmental impact while maintaining deposition quality. The presence of BaCO3 in the films was proven using X-ray diffraction. Other impurities such as TiO2 and NiO were not detected. A significant variation in the average grain size was not observed for films with different thicknesses whereas films sintered at different temperatures displayed greater variation. A bimodal pore size distribution in the samples suggested that the powder was agglomerated after deposition due to a high deposition voltage (20 V). Rapid deposition times of 2 to 8 seconds offered a potential for cost reduction compared to longer deposition times implemented in industry. Therefore the increased porosity was accepted. The dielectric constant of the films increased from 2900 to 6730 as the thickness increased from 17.75 µm to 47.5 µm. The dissipation factor decreased from 0.27 to 0.06 with increasing thickness. This behavior was attributed to a low dielectric constant interfacial layer and a higher dielectric leakage current at smaller thicknesses. The dielectric constant increased from 1700 to 6350 and the dissipation factor decreased from 0.23 to 0.04 as the sintering temperature increased from 1150°C to 1300°C. This was attributed to an increase in tetragonality with grain size and a decrease in porosity with sintering temperature. Finally, etching a substrate for 60 seconds increased its capacitance by 27.47% and using ultrasonic agitation further increased the capacitance by 8.75%. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2012-10-12 00:54:53.915

A partir de l'étude des effets de la chimie de surface des Nanodiamants (NDs) sur leurs propriétés électroniques, cette thèse a permis la mise en évidence d'un effet thérapeutique des NDs sur des cellules humaines. En particulier, il a été montré que les NDs de détonation peuvent générer des radicaux libres oxygénés sous radiation ionisante, ce qui pourrait améliorer l'efficacité de certains traitements de radiothérapie actuels. Les échanges électroniques entre le coeur des NDs et leur environnement sont en effet favorisés après des traitements de surface, notamment d'hydrogénation et de graphitisation de surface. Les conditions expérimentales permettant d'obtenir des NDs hydrogénées (NDs-H) sous plasma d'hydrogène ont été optimisées sous ultravide, puis ont été utilisées pour préparer de grandes quantités de NDs-H sous forme pulvérulente. La même procédure a été appliquée pour la graphitisation de surface des NDs, en utilisant des recuits sous vide à haute température. L'effet de ces traitements de surface sur les propriétés d'interactions électroniques des NDs a été étudié après exposition à l'air ambiant, puis en dispersion dans l'eau. Ces traitements de surface assurent notamment un potentiel Zeta positif aux NDs, dont l'origine a été discutée. Enfin, les interactions des NDs avec plusieurs lignées de cellules tumorales humaines ont été étudiées et l'efficacité des NDs pour radiosensibiliser des cellules radiorésistantes sous irradiation gamma a été montrée, ouvrant de nouvelles perspectives d'applications des NDs en nanomédecine. . / In this thesis, a therapeutic effect of nanodiamonds (NDs) has been evidenced by investigating the role of NDs surface chemistry on their electronic properties. More precisely, the generation of reactive oxygen species from detonation NDs under ionizing radiation, which could improve current radiotherapy treatments, has been demonstrated. To this end, surface treatments facilitating electron transfer from NDs to their environment, namely hydrogenation and surface graphitization, were developed. Experimental conditions ensuring an efficient hydrogenation by hydrogen plasma were determined under ultrahigh vacuum, before being used to prepare large quantities of NDs in powder phase. A similar procedure was applied to the surface graphitization of NDs, performed by annealing under vacuum at high temperature. The impact of such surface treatments on the electronic interaction properties of NDs has been investigated under ambient air and after dispersion in water. These surface treatments induce a positive Zeta potential to NDs in water, which origin has been discussed. Finally, their interactions with human tumor cells were observed. Radiosensitization of tumor cells using NDs under gamma irradiation was demonstrated, opening new perspectives for NDs in nanomedicine.