Manufactured nanomaterials (MNMs) from the rapidly increasing number of consumer products that contain MNMs are being discharged into waste streams. Increasing evidence suggests that several classes of MNMs may accumulate in sludge derived from wastewater treatment and ultimately in soil following land application as biosolids. Little research has been conducted to evaluate the impact of MNMs on terrestrial ecosystems, despite the fact that land application of biosolids from wastewater treatment will be a major pathway for the introduction of MNMs to the environment. To begin addressing this knowledge gap, we have conducted a series of experiments designed to test how bioavailable MNMs are to terrestrial ecoreceptors when exposed through a variety of pathways. First, we used the model organisms Nicotiana tabacum L. cv Xanthi (tobacco) and Triticum aestivum (wheat) to investigate plant uptake of 10, 30 and 50 nm diameter gold (Au) MNMs coated with either tannate (T-MNMs) or citrate (C-MNMs). Both C-MNMs and T-MNMs of each size treatment bioaccumulated in tobacco, but no bioaccumulation of MNMs was observed for any treatment in wheat. In a second exposure, we investigated the potential for bioaccumulation of MNMs from contaminated plant surfaces by a terrestrial secondary consumer, tobacco hornworm (Manduca sexta). We found that hornworms bioaccumulate Au MNMs, but that the assimilation efficiency of bioaccumulation was low. Hornworms eliminate ingested Au MNMs rapidly from 0-24 h, but very slowly from 1 d to 7 d. Finally, we used the model organisms tobacco and tobacco hornworm to investigate the potential for trophic transfer of Au MNMs. Biomagnification of Au MNMs was observed in the hornworms. We have demonstrated that MNMs of a wide range of size and with different surface chemistries are bioavailable to plants, that MNMs resuspended by wind, rain, biota, and mechanical disturbance from soil onto plant surfaces are bioavailable to terrestrial consumers, and that trophic transfer and biomagnification of plant accumulated MNMs can occur. These results have important implications for risks associated with nanotechnology, including the potential for human exposure.

Foam has been used as a mobility control technique in CO₂ flooding to improve volumetric sweep efficiency. Stabilizing CO₂ foam with nanoparticle instead of surfactant has some notable advantages. Nanoparticle-stabilized foam is very stable because a large adsorption energy is required to bring nanoparticles to the bubble interfaces. As a solid, nanoparticle can potentially withstand the high temperature in the reservoir, providing a robust foam stability for an extended period of time. The ability of nanoparticles to generate foam only above a threshold shear rate is promising as foam can be engineered to form only in the high permeability zone. These nanoparticles are hundreds of times smaller than pore throats and thus can travel in the reservoir without plugging the pore throats. Surface-modified silica nanoparticle was found to stabilize CO₂ -in-water foam at temperature up to 80 ˚C and salinity as high as 7.2 wt%. The foam was generated through the co-injection of aqueous nanoparticle dispersion and CO₂ into consolidated rock cores, primarily sandstones, with and without an induced fracture in the core. A critical shear rate for foam generation was found to exist in both matrix and fracture, however, this critical rate varied with the experiment conditions. The effects of experimental parameters on the critical shear rate and foam apparent viscosity were also investigated. Additionally, the flow distribution calculation in fractured sandstone cores revealed a diversion of flow from fracture toward matrix once foam was generated, suggesting conformance control potential in fractured reservoirs. In order to study foam rheology, high-permeability beadpack was installed upstream of the core to serve as a foam generator. This allows the foam mobility to be measured solely while being transported through the core, without the complicating effect of transient foam generation in the core. The injection of the pre-generated foam into the core at residual oil condition was found to reduce the residual oil saturation to the same level as CO₂ flood, however, with the advantage of mobility control. The 'coalescence-regeneration' mechanism of foam transport in porous media possibly allowed the foam's CO₂ to contact and mobilize the residual oil. The injection of the foam slug followed by a slug of only CO₂ was also tested, showing similar viscosification as the continuous foam injection, however, required less nanoparticles. / text

For two decades, single-wall carbon nanotubes (SWCNTs) have captured the attention of the research community, and become one of the flagships of nanotechnology. Due to their remarkable electronic and optical properties, SWCNTs are prime candidates for the creation of novel and revolutionary electronic, medical, and energy technologies. However, a major stumbling block in the exploitation of nanotube-based technologies is the lack of control of nanotube structure (chirality) during synthesis, which is intimately related to the metallic or semiconductor character of the nanotube. Incomplete understanding of the nanotube growth mechanism hinders a rationale and cost-efficient search of experimental conditions that give way to structural (chiral) control. Thus, computational techniques such as density functional theory (DFT), and reactive molecular dynamics (RMD) are valuable tools that provide the necessary theoretical framework to guide the design of experiments. The nanotube chirality is determined by the helicity of the nanotube and its diameter. DFT calculations show that once a small nanotube 'seed' is nucleated, growth proceeds faster if the seed corresponds to a high chiral angle nanotube. Thus, a strategy to gain control of the nanotube structure during chemical vapor deposition synthesis must focus on controlling the structure of the nucleated nanotube seeds. DFT and RMD simulations demonstrate the viability of using the structures of catalyst particles over which nanotube growth proceeds as templates guiding nanotube growth toward desired chiralities. This effect occurs through epitaxial effects between the nanocatalyst and the nanotube growing on it. The effectiveness of such effects has a non-monotonic relationship with the size of the nanocatalyst, and its interaction with the support, and requires fine-tuning reaction conditions for its exploitation. RMD simulations also demonstrate that carbon bulk-diffusion and nanoparticle supersaturation are not needed to promote nanotube growth, hence reaction conditions that increase nanoparticle stability, but reduce carbon solubility, may be explored to achieve nanotube templated growth of desired chiralities. The effect of carbon dissolution was further demonstrated through analyses of calculated diffusion coefficients. The metallic nanocatalyst was determined to be in viscous solid state throughout growth, but with a less solid character during the induction/nucleation stage.

Polymer hydrogel films change their properties in response to environmental change. This remarkable phenomenon results in many potential applications of polymer hydrogel films. In this thesis colored thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel film was prepared by firstly synthesizing polymer latex and secondarily crosslinking the nanoparticles and casting the polymers onto glass. The shape-memory effect has been observed when changing the environmental temperature. The temperature-dependent of turbidity of polymer hydrogel film was measured by HP UVVisible spectrophotometer. This intelligent hydrogel might be used in chemomechanical systems and separation devices as well as sensors. Polymer adsorption plays an important role in many products and processes. In this thesis, surfactant-free three-dimensional polystyrene (PS) nanoparticle network has been prepared. The infrared spectroscopy and solubility experiment are performed to prove the crosslinking mechanism, also the BET method was used to measure the adsorption and desorption of polystyrene network. The BET constant (C) is calculated (C=6.32). The chemically bonded polymer nanoparticle network might have potential applications as catalyst or used for chromatographic columns.

The thermally responsive hydroxypropyl cellulose (HPC) hydrogel nanoparticles have been synthesized and characterized. The HPC particles were obtained by chemically crosslinking collapsed HPC polymer chains in water-surfactant (dodecyltrimethylammonium bromide) dispersion above the lower critical solution temperature (LCST) of the HPC. The size distributions of microgel particles, measured by dynamic light scattering, have been correlated with synthesis conditions including surfactant concentration, polymer concentration, and reaction temperature. The swelling and phase transition properties of resultant HPC microgels have been analyzed using both static and dynamic light scattering techniques. By first making gel nanoparticles and then covalently bonding them together, we have engineered a new class of gels with two levels of structural hierarchy: the primary network is crosslinked polymer chains in each individual particle, while the secondary network is a system of crosslinked nanoparticles. The covalent bonding contributes to the structural stability of the nanostructured gels, while self-assembly provides them with crystal structures that diffract light, resulting in colors. By using N-isopropylacrylamide copolymer hydrogel nanoparticles, we have synthesized nanoparticle networks that display a striking iridescence like precious opal but are soft and flexible like gelatin. This is in contrast to previous colored hydrogels, which were created either by adding dyes or fluorescent, or by organic solvent or by embedding a colloidal crystal array of polymer solid spheres . Creating such periodic 3D structures in materials allows us to obtain useful functionality not only from the constituent building blocks but also from the long-range ordering that characterizes these structures. Hydroxypropyl cellulose (HPC) and poly (acrylic acid ) (PAA) complexes were studied using turbidity measurement and laser light scattering. The phase transition temperature of the complexes is found to depend on pH and molecular weights of PAA and HPC. The driving force for this phenomenon is due to the hydrogen bonding and hydrophobic interaction of the macromolecules. Based on the principle of the PAA/HPC complexes, the PAA nanoparticles were synthesized in 0.1wt % HPC aqueous solution at room temperature.

Substances that consist of nano-scale fillers dispersed in a polymer matrix are known as polymer-nanocomposites (PNCs). These materials are appealing since they have high potentials for applications, due to their mechanical, electrical, and thermo electrical properties. A common problem associated with PNCs is that the nano-fillers have a tendency to aggregate into clusters and form phase separated domains, which cause the desired properties of the system to either diminish or vanish all together. Hairy nanoparticles (HNPs) can avoid the issue of agglomeration that is commonly encountered by conventional PNCs. When polymer chains are grafted to a nanoparticle, and the coverage is high, the nanoparticles have decreased inter-particle interactions which allows for enhanced dispersion and mixing into a polymer matrix. By tailoring the architecture (functionalization of polymer chains, degree of polymerization, grafting density) of HNPs, it is possible to control the final properties of the system. An in depth study was carried out to investigate the effects of hairy-nanoparticle architecture on the resulting properties of the material itself. Atom transfer radical polymerization and living anionic polymerization were used to synthesize the polymer chains, of the HNP systems, while various instrumental methods including differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were utilized to study the physical ageing affects and self-assembly of these systems. #88ABW-2015-4971

Mantle cell lymphoma (MCL) is an extremely difficult to treat subtype of non-Hodgkin lymphoma (NHL) with a low patient survival rate compared to most common cancers. Recently, nanoparticle delivery systems have received a great deal of interest for treating NHL. One of the more promising cargo options for these systems is short interfering RNA (siRNA). siRNA is a 18-23 nucleotide long double stranded RNA that is used to inhibit the protein expression of target mRNAs in a sequence specific manner. MCLs have several commonly overexpressed genes compared to normal cells making it an ideal candidate for siRNA therapies. For RNA interference to occur, A delivery vehicle is needed for the siRNA to reach the cytoplasm of the cell. In this thesis, ionizable lipid-like materials termed lipidoids are formulated into lipid nanoparticles (LNPs) to deliver siRNA. A new library of lipidoids is constructed to gain a better understanding of how the lipidoid tail-structure affects the silencing ability of LNPs. A novel tail precursor is identified as conferring potency to LNPs. Then, LNPs are used to silence genes within difficult to transfect MCL cells. LNPs targeting the anti-apoptotic protein Mcl-1 exhibit potent gene silencing and cause an increase in the fraction of cells undergoing apoptosis. This is important because there is no therapeutic that is FDA approved that targets this commonly overexpressed protein. Because of this LNP’s potency, siRNAs targeting multiple genes can be encapsulated into LNPs without causing unwanted toxicity. LNPs targeting several genes in multiple pathways cause a larger fraction of MCL cells to undergo apoptosis compared to cells treated with LNPs targeting only one gene. A major issue in cancer therapeutics is that the majority of nanoparticles accumulate in the liver. In an effort to improve the delivery of LNPs to target cells, changes to their formulations and administration methods are investigated as a means to improve LNP circulation time, biodistribution, and silencing ability. Overall, this work identifies lipidoid nanoparticles as potent siRNA delivery systems to treat MCL and investigates key properties for further improvement in LNP siRNA delivery to target cells.

Lanthanide-based nanoparticles can be used in a variety of applications, including biomedical work such as imaging and cancer therapies, and in solar cells. This thesis presents two different potential applications for lanthanide-based nanoparticles and a possible new method for single nanoparticle analysis. Each of the projects presented in this thesis starts from the colloidal synthesis of the nanoparticles and then explores their varying properties, such as size and size distribution, crystallinity, elemental composition, and optical properties. Chapter 1 presents a short introduction to lanthanides and explores their ability to luminesce and upconvert. These optical properties make lanthanide-based nanoparticles attractive in both the visible and near-infrared (NIR) range. Chapter 2 explores the possibility of using β-LaF3:Nd3+ (5%) nanoparticles in a colloidal laser to overcome some issues that solid state lasers face due to thermal effects. A colloidal laser requires small nanoparticles that can emit a useful wavelength and that are dispersed in a high boiling point liquid. In Chapter 3, a cation exchange of ytterbium for yttrium and erbium in water-dispersible β-NaYF4:Er3+ nanoparticles across a polyvinylpyrrolidone (PVP) surface coating was tested as a possible synthesis route for radioactive nanoparticles. Incorporating radioactive materials at the end of a therapy preparation would limit the number of synthesis steps in an isotope laboratory. Chapter 4 presents single-particle analysis of β-NaYF4:Er3+ (50%) nanoparticles using X-ray absorption spectroscopy (XAS) at the Canadian Light Source (CLS). Electron beams in scanning electron transmission microscopes (STEM) can damage the samples, making quantification of nanoparticles challenging. Finally, Chapter 5 discusses some conclusions and suggests possible future work. / Graduate / 0494

Modification of nanostructures via laser processing is of great interest for a wide range of applications such as aerospace and the storage of nuclear waste. The primary goal of this dissertation is to improve the understanding of nanostructures through two primary routes: the modification of aerogels and pulsed laser ablation in ethanol. A new class of materials, patterned aerogels, was fabricated by photopolymerizing selected regions of homogeneous aerogel monoliths using visible light. The characterization and fabrication of functionally graded, cellular and compositionally anisotropic aerogels and ceramics is discussed. Visible light was utilized due to it’s minimal absorption and scattering by organic molecules and oxide nanoparticles within wet gels. This allowed for the fabrication of deeply penetrating, well resolved patterns. Similarly, nanoporous monoliths with a typical aerogel core and a mechanically robust exterior ceramic layer were synthesized from silica aerogels cross-linked with polyacrylonitrile. Simple variations of the exposure geometry allowed fabrication of a wide variety of anisotropic materials without requiring layering or bonding. Nanoparticle solutions were prepared by laser ablation of metal foils (Fe and Mo) in ethanol. Ablation of Fe generated Fe3O4 and Fe3C nanoparticles which were superparamagnetic with a saturation magnetization Ms = 124 emu/g. Zero field cooled (ZFC) measurements collected at an applied field of 50 Oe displayed a maximum magnetic susceptibility at 120 K with a broad distribution. Field cooled (FC) measurements showed a thermal hysteresis indicative of temperature dependent magnetic viscosity. Pulsed laser ablation of a Mo foil in ethanol generated inhomogeneous nanoparticles where Mo and MoC coexisted within the same aggregate. Formation of these unique nanoparticles is likely due to phase separation that occurs when a high temperature carbide phase cools after the laser pulse terminates. Similarly, magnetic nanoparticle suspensions were generated by pulsed laser ablation of Fe and Mo in ethanol. The formation of several carbide phases with no discernable alloy formation was seen. A decrease in magnetization with a decrease in Fe concentration was seen which was reconciled with the decreased Fe content in the system. However, at Fe concentrations below ~ 40%, an increase in Ms and Hc was observed which was reconciled with the disappearance of the ε–Fe3C. TEM analysis showed the formation of core-shell nanoparticles and Energy Filtered TEM showed the distribution of Fe-based nanoparticles in the suspensions.

The sizes of nonionic reverse micelles were investigated as a function of the molecular structure of the surfactant, the type of oil, the total concentration of surfactant [NP], the ratio of NP4 to total surfactant (r), the water to surfactant molar ratio (ω), temperature, salt concentration, and polar phase. The basis of our investigation was nonylphenol polyethoxylates - NP4 and NP7. Micelle sizes were determined using dynamic light scattering (DLS). A central composite experimental design was used to quantitatively model reverse micelle size as a function of ω, [NP], and r. The model has demonstrated the capability of predicting the mean diameter of micelles from 4 to 13 nm with a precision of ± 2 nm as measured by DLS. This quantitative correlation between the size of reverse micelles and the synthetic variables provides the foundation for choosing experimental conditions to control reverse micelle size.