Photocatalytic oxidation is an alternative water treatment method under consideration for disinfecting water. Chlorine disinfection can form harmful byproducts, and some viruses (e.g. adenoviruses) are resistant to other alternative disinfection methods. Photocatalytic oxidation using nano-sized photocatalytic particles (e.g. TiO2, fullerene) holds promise; however, it is limited by its low efficiency and long required treatment times. This research focuses on improving virus inactivation by photocatalytic oxidation by modifying catalysts for improved activity, by analyzing virus inactivation kinetics, and by elucidating the inactivation mechanisms of adenovirus serotype 2 (AdV2) and bacteriophage MS2. Modifying TiO2 with silver (nAg/TiO2) or silica (SiO2-TiO2) improves the inactivation kinetics of bacteriophage MS2 by a factor of 3-10. nAg/ TiO2 increases hydroxyl radical (HO•) production while SiO2 increases the adsorption of MS2 to TiO2. These results suggest that modifying the photocatalyst surface to increase contaminant adsorption is an important improvement strategy along with increasing HO• production. The inactivation kinetics of AdV2 by P25 TiO2 is much slower than the MS2 inactivation kinetics and displays a strong shoulder, which is not present in the MS2 kinetics. nAg/TiO2 initially improves the inactivation rate of AdV2. SiO2-TiO2 reduces the AdV2 inactivation kinetics since adsorption is not significantly enhanced, as it is with MS2. Amino-C60 is highly effective for AdV2 inactivation under visible light irradiation, making it a good material for use in solar disinfection systems. The efficacy of amino-fullerene also demonstrates that singlet oxygen is effective for AdV2 inactivation. When exposed to irradiated TiO2, AdV2 hexon proteins are heavily damaged resulting in the release of DNA. DNA damage is also present but may occur after capsids break. With MS2, the host interaction protein is rapidly damaged, but not the coat protein. The kinetics of MS2 inactivation are rapid since it may quickly lose its ability to attach to host cells, while AdV2 kinetics are slower since the entire capsid must undergo heavy oxidation before inactivation occurs. Adenovirus inactivation likely occurs through breaching the capsid followed by radical attack of DNA and core proteins.

Photocatalytic oxidation is an alternative water treatment method under consideration for disinfecting water. Chlorine disinfection can form harmful byproducts, and some viruses (e.g. adenoviruses) are resistant to other alternative disinfection methods. Photocatalytic oxidation using nano-sized photocatalytic particles (e.g. TiO2, fullerene) holds promise; however, it is limited by its low efficiency and long required treatment times. This research focuses on improving virus inactivation by photocatalytic oxidation by modifying catalysts for improved activity, by analyzing virus inactivation kinetics, and by elucidating the inactivation mechanisms of adenovirus serotype 2 (AdV2) and bacteriophage MS2. Modifying TiO2 with silver (nAg/TiO2) or silica (SiO2-TiO2) improves the inactivation kinetics of bacteriophage MS2 by a factor of 3-10. nAg/ TiO2 increases hydroxyl radical (HO•) production while SiO2 increases the adsorption of MS2 to TiO2. These results suggest that modifying the photocatalyst surface to increase contaminant adsorption is an important improvement strategy along with increasing HO• production. The inactivation kinetics of AdV2 by P25 TiO2 is much slower than the MS2 inactivation kinetics and displays a strong shoulder, which is not present in the MS2 kinetics. nAg/TiO2 initially improves the inactivation rate of AdV2. SiO2-TiO2 reduces the AdV2 inactivation kinetics since adsorption is not significantly enhanced, as it is with MS2. Amino-C60 is highly effective for AdV2 inactivation under visible light irradiation, making it a good material for use in solar disinfection systems. The efficacy of amino-fullerene also demonstrates that singlet oxygen is effective for AdV2 inactivation. When exposed to irradiated TiO2, AdV2 hexon proteins are heavily damaged resulting in the release of DNA. DNA damage is also present but may occur after capsids break. With MS2, the host interaction protein is rapidly damaged, but not the coat protein. The kinetics of MS2 inactivation are rapid since it may quickly lose its ability to attach to host cells, while AdV2 kinetics are slower since the entire capsid must undergo heavy oxidation before inactivation occurs. Adenovirus inactivation likely occurs through breaching the capsid followed by radical attack of DNA and core proteins.

It was hypothesized that superparamagnetic nanoparticles encapsulated in a silica shell with a fluorescent dye could be functionalized with axonal tracers and could be used for serial, non-invasive imaging with magnetic resonance imaging (MRI) for axon tract tracing. Nanoparticles functionalized with amine, octadecyl, silica, and biotinylated dextran amine were manufactured and characterized with MRI, scanning electron microscopy, and UV-visible, infrared, and fluorescence spectroscopy. Nanoparticle concentrations of 10 mM were not toxic to adult rat neural progenitor cells (NPCs) and labeled approximately 90% of cells. Nanoparticles were assessed for anterograde and retrograde tract tracing in adult rat models. With MRI and microscopy, the nanoparticles did not appear to trace axons but did provide an MRI signal for up to 3 weeks post implantation. While functionalized nanoparticles did not appear to trace axons, they are not toxic to NPCs and may be used as a MRI contrast agent in the neural axis.

Studies various nanostructured materials have gained considerable interest within the past several decades. This novel class of materials has opened up a new realm of possibilities, both for the fundamental comprehension of matter, but also for innovative applications. The size-dependent effect observed for these systems often lies in their interaction with the surrounding environment and understanding such interactions is the pivotal point for the investigations undertaken in this thesis. Three families of nanoparticles are analyzed: semiconductor quantum dots, metallic silver nanoparticles and rare-earth oxide nanomaterials. The radical scavenging ability of cerium oxide nanoparticles (CeO2) is quite controversial since they have been labeled as both oxidizing and antioxidant species for biological systems. Here, both aqueous and organic stabilized nanoparticles are examined in straightforward systems containing only one reactive oxygen species to ensure a controlled release. The apparent absence of their direct radical scavenging ability is demonstrated despite the ease at which CeO2 nanoparticles generate stable surface Ce3+ clusters, which is used to explain the redox activity of these nanomaterials. On the contrary, CeO2 nanoparticles are shown to have an indirect scavenging effect in Fenton reactions by annihilating the reactivity of Fe2+ salts. Cadmium selenide quantum dots (CdSe QD) constitute another highly appealing family of nanocolloids in part due to their tunable, size-dependent luminescence across the visible spectrum. The effect of elemental sulfur treatment is investigated to overcome one of the main drawbacks of CdSe QD: low fluorescence quantum yield. Herein, we report a constant and reproducible quantum yield of 15%. The effect of sulfur surface treatment is also assessed following the growth of a silica shell, as well as the response towards a solution quencher (4-amino-TEMPO). The sulfur treated QD is also tested for interaction with pyronin Y, a xanthene dye that offers potential energy and electron transfer applications with the QD. Interaction with the dye molecule is compared to results obtained with untreated quantum dots, as well as CdSe/ZnS core shell examples. In another chapter of this thesis, the catalytic potential of silver nanoparticles is addressed for the grafting of polyhydrosiloxane polymer chains with various alkoxy groups. A simple one-pot synthesis is presented with silver salts and the polymer. the latter serves as a mild reducing agent and a stabilizing ligand, once silver nanoparticles are formed in-situ. We evaluate the conversion of silane into silyl ethers groups with the addition of several alcohols, whether primary, secondary or tertiary, and report the yields of grafting under the mildest conditions: room temperature, under air and atmospheric pressure.

This thesis focuses on pioneering a scalable route to fabricate quantum information devices based upon single InAs/InP quantum dots emitting in the telecommunications wavelength band around 1550 nm. Using metallic gates in combination with nanotemplate, site-selective epitaxy techniques, arrays of single quantum dots are produced and electrostatically tuned with a high degree of control over the electrical and optical properties of each individual quantum dot. Using metallic gates to apply local electric fields, the number of electrons within each quantum dot can be tuned and the nature of the optical recombination process controlled. Four electrostatic gates mounted along the sides of a square-based, pyramidal nanotemplate in combination with a flat metallic gate on the back of the InP substrate allow the application of electric fields in any direction across a single quantum dot. Using lateral fields provided by the metallic gates on the sidewalls of the pyramid and a vertical electric field able to control the charge state of the quantum dot, the exchange splitting of the exciton, trion and biexciton are measured as a function of gate voltage. A quadrupole electric field configuration is predicted to symmetrize the product of electron and hole wavefunctions within the dot, producing two degenerate exciton states from the two possible optical decay pathways of the biexciton. Building upon these capabilities, the anisotropic exchange splitting between the exciton states within the biexciton cascade is shown to be reversibly tuned through zero for the first time. We show direct control over the electron and hole wavefunction symmetry, thus enabling the entanglement of emitted photon pairs in asymmetric quantum dots. Optical spectroscopy of single InAs/InP quantum dots atop pyramidal nanotemplates in magnetic fields up to 28T is used to examine the dispersion of the s, p and d shell states. The g-factor and diamagnetic shift of the exciton and charged exciton states from over thirty single quantum dots are calculated from the spectra. The g-factor shows a generally linear dependence on dot emission energy, in agreement with previous work on this subject. A positive linear correlation between diamagnetic coefficient and g-factor is observed.

The search for cellulosic based products as a viable alternative for petroleum-based products was the impetus for covalently crosslinking lignocellulosic fibers and nanocellulose whiskers with poly(methyl vinyl ether) co maleic acid (PMVEMA) - polyethylene glycol (PEG). The lignocellulosics used were ECF bleached softwood (pine) and ECF bleached birch kraft pulp. This thesis also tests the hypothesis that water absorption and retention can be improved by grafting PMVEMA-PEG to the surface of ECF bleached kraft pulp hardwood and softwood fibers via microwave initiated crosslinking. The crosslinking of the PMVEMA to hardwood and softwood kraft ECF bleached pulp fibers resulted in enhanced water absorbing pulp fibers where the PMVEMA is grafted onto the surface of the fibers. The crosslinking was initiated both thermally and via microwave irradiation and the water absorption and water retention was measured as the percent of grafted PMVEMA. This was the first application of microwave crosslinking of pulp fibers with the goal of creating water absorbing pulp fibers. Ultimately, the water absorption values ranged from 28.70 g water per g dry crosslinked pulp fiber (g/g) to 230.10 g/g and the water retention values ranged from 26% to 71% of the water retained that was absorbed by the crosslinked pulp fibers. The microwave initiated crosslinked fibers had comparable results to the thermally crosslinked fibers with a decreased reaction time, from 6.50 min (thermal) to 1 min 45 sec (microwave). Cellulose nanowhiskers, crystalline rods of cellulose, have been investigated due to their unique properties, such as nanoscale dimensions, low density, high surface area, mechanical strength, and surface morphology and available surface chemistry. Prior to this study, the crosslinking of cellulose whiskers with the matrix via solution casting of liquid suspensions of whiskers and matrix had not been explored. The hypothesis to be investigated was that incorporating cellulosic whiskers with the PMVEMA-PEG matrix and crosslinking the whiskers with the matrix would yield films that demonstrate unique properties when compared to prior work of crosslinking of PMVEMA-PEG to macroscopic ECF bleached kraft pulp fibers. Solution cast composites of cellulose nanowhiskers-PMVEMA-PEG were crosslinked at 135 °C for 6.5 min and analyzed for crosslinking, thermal stability, strength and mechanical properties, whisker dispersion, and water absorption and uptake rates. The whisker-composites demonstrated unique properties upon crosslinking the whiskers with PMVEMA-PEG, especially the elongation at break and tensile strength upon conditioning of the final materials at various relative humidities. In addition, the whiskers improved the thermal stability of the PMVEMA-PEG matrix. This is significant as methods of improving processing thermal stability are key to developing new materials that utilize cellulose whiskers, PMVEMA, and PEG. This thesis addresses the hypothesis that cellulose nanowhiskers that are crosslinked with a matrix can create new whisker-matrix composites that behave differently after crosslinking.

Dreamhome is a creative exploration of a prototype house designed with creative freedom using possible future technologies that may not be currently feasible. New and forthcoming technology in various scientific branches that could be applicable to architecture will be presented, and the applications discussed. Limitations of application to architecture of the reviewed technologies will be discussed. Prior works by architects and engineers who push boundaries to innovatively overcome technological limitations will be explored, as will examples in which advanced technology is applied to create unique architectural designs. Together these references will evoke inspirations to be translated into an architectural design and a virtual home. The house is desired to boast of a unique design with various aesthetic and functional features that are not usually seen in present day architecture. This visualization could be a glimpse of possible home design of the future.

Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, can be likened to semiconductors because of small band gaps and low electronic mobility. CPs are exploited as an excellent tool for the preparation of nanocomposites with nano scaled biomolecules. Polypyrrole (Ppy) was the first of this key family of compounds to show high conductivity. So, electrically conducting polypyrrole (Ppy) has numerous applications. In this study, caffeine imprinted electrodes (CIE) were prepared and characterized. This research project mainly focused on three important aspects: &#;To determine the thickness of the polymeric film. &#;To determine the Limit of detection (LOD) of the polymeric film at different conditions. &#;To determine the Analytical Sensitivity (γ) of the polymeric film at varied conditions. In summary these are conclusions stated: •The thickness of the electrode increased with an increase in the number of pulses. The film thickness increased linearly up to an application of 30 pulses and after 30 pulses, an increase in slope occurred with again a linear correlation up to the maximum applied number of pulses, 42. This change in slope may indicate a different mechanism taking place. •LOD is improved as the caffeine load is reduced from 10.0 to 3.0 mM and as the number of pulses is reduced from 36 to 24. •γ increases the number of pulses increase from 24 to 36 and also increases as the caffeine load increases.

There is an increased interest in understanding the toxicity and rational design of gold nanoparticles (GNPs) for biomedical applications in recent years. Such efforts warrant reliable, viable, and biofriendly synthetic methodology for GNPs with homogeneous sizes and shapes, particularly sizes above 30 nm, which is currently challenging. In the present study, an environmentally benign, biofriendly, singlestep/ single-phase synthetic method using dextrose as a reducing and capping agent in a buffered aqueous solution at moderate temperature is introduced. The resulting GNPs are near-spherical, stable, catalytically active, place exchangeable, and water-soluble within the size range of 10-120 nm. The added advantage of the biologically friendly reaction medium employed in this new synthetic approach provides a method for the direct embedment/integration of GNPs into biological systems such as the E. coli bacterium without additional capping ligand or surface modification processes.

It was hypothesized that superparamagnetic nanoparticles encapsulated in a silica shell with a fluorescent dye could be functionalized with axonal tracers and could be used for serial, non-invasive imaging with magnetic resonance imaging (MRI) for axon tract tracing. Nanoparticles functionalized with amine, octadecyl, silica, and biotinylated dextran amine were manufactured and characterized with MRI, scanning electron microscopy, and UV-visible, infrared, and fluorescence spectroscopy. Nanoparticle concentrations of 10 mM were not toxic to adult rat neural progenitor cells (NPCs) and labeled approximately 90% of cells. Nanoparticles were assessed for anterograde and retrograde tract tracing in adult rat models. With MRI and microscopy, the nanoparticles did not appear to trace axons but did provide an MRI signal for up to 3 weeks post implantation. While functionalized nanoparticles did not appear to trace axons, they are not toxic to NPCs and may be used as a MRI contrast agent in the neural axis.