Thesis--University of California, Berkeley, 1961. / "UC-4 Chemistry General" -t.p. "TID-4500 (16th Ed.)" -t.p. Includes bibliographical references (p. 98-99).

Inaug.-diss.--Leipzig. / Lebenslauf.

Thesis (Ph. D.)--University of Delaware, 2006. / Principal faculty advisor: Mark A. Barteau, Dept. of Chemical Engineering. Includes bibliographical references.

Thesis (doctoral) -- Uppsala universitet, 1781. / Reproduction of original from Kress Library of Business and Economics, Harvard University. Goldsmiths'-Kress no. 12138.0-2.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 200-218).

It is of fundamental significance to differentiate an enantiomer from its mirror image (i.e., enantiodifferentiation), through monitoring optical activity (OA) of enantiomers that is typically characterized by electronic circular dichroism (ECD or CD) in the UV-visible region. However, sub-wavelength molecular dimensions substantially prevent enantiomers from effectively perceiving the different circular polarization states, leading to low enantiomeric OA and weak enantiodifferentiation. Some approaches have been developed to amplify the enantiomeric OA; alternatively, on the basis of the emerging chiral metamaterials of metallic helical nanoparticles (HNPs) I devise two methods to enhance the enantiodifferentiation. First, I employ glancing angle deposition (GLAD) to deposit Ag HNPs with a helical pitch (P) larger than wire diameter (d) of the helical, i.e., Ag nanohelices (AgNHs). AgNHs exhibit strong plasmonic CD composed of a broadband longitudinal mode (i.e., L-mode) in the visible region, a transverse mode (i.e., T-mode) at a wavelength of ~370 nm, and a dielectric mode in the deep UV region (at a wavelength shorter than 320 nm). Adsorption of alkyl ligands on the AgNHs markedly weakens the two plasmonic CD modes, and the T-mode is weakened more seriously than the L-mode. The deterioration of the plasmonic CD is exacerbated with increasing the bonding energy of the Ag-alkyl ligand contacts, attributed to the increase of the dielectric constant of the medium of the AgNHs (εr) and the electron withdrawal from the AgNHs towards the alkyl ligands. Derived from the ligand-induced weakening of the plasmonic CD, enantiodifferentiation of L-Glutathione (L-GSH) from D-GSH is dramatically enhanced. The chiroptical weakening sensitively varies with the absolute configuration of GSH, resulting in an enantiodifferentiation anisotropic g factor of ~0.5 that is independent on the AgNH helicity. The AgNH-induced anisotropy g factor is superior to those obtained by other methods, by 2 - 4 orders of magnitude. It is the largest achieved up-to-date, as high as one-fourth of the theoretical maximum. Second, I operate GLAD with fast substrate rotation to reduce P less than d, to generate AgHNPs that exhibit negligible dielectric CD in the deep UV region, offering a helical substrate to directly amplify the OA of enantiomers grafted on the AgHNPs. The anchoring of enantiomers on AgHNPs with the sub-5 nm P leads to the enantioselective amplification of the enantiomeric OA in roughly ten folds; the LH- and RH-AgHNPs give rise to amplify the OA of (S)- and (R)-enantiomers, respectively. It is ascribed to the change of the dihedral angle of an enantiomer adsorbed on AgHNPs. Such the enantioselective amplification tends not to occur as long as P > 5 nm. Moreover, given the enantiodifferentiation of biomolecules that are typically dissolved in an aqueous solution, the effect of water on the plasmonic CD of AgHNPs is investigated and compared with that of AgNHs. Hydrophobic AgNHs with high structural porosity give rise to the irreversible water effect on the plasmonic CD; and hydrophilic AgHNPs with low structural porosity lead to the reversible water effect. At the end, I devise a new methodology to generate plasmonic CD through chirality transfer from chiral host to achiral guest, owing to the helicity duplication of the achiral guest from the chiral host. It leads to inducing chiroptical activity of the achiral guest made of some plasmonic materials that aren't facilely sculptured in the helical. The new methodology effectively broadens the range of materials made from the chiral nanostructures, which is on demand to develop diverse chirality-related bioapplications.

Engineered nanomaterials (ENMs) are currently used in a wide range of manufacturing processes and applications thanks to the numerous technical and economic benefits derived from the incorporation of ENMs in these processes. Accompanying these benefits are the potential toxicity of ENMs to humans and the environment. Previous research has shown that ENMs display strong toxicity to plants. Earlier research suggested that physicochemical properties of ENMs such as their size, shape, and surface properties considerably affect toxicity; however, the unique physicochemical properties of ENMs affect their phytotxicity to plants is still unknown. This research evaluated the phytotoxicity of silver and gold nanoparticles to lettuce plants in both sand and hydroponic conditions by monitoring a wide range of plant physiological parameters after their exposure to these nanoparticles with two coating materials (citrate and polyvinylpyrrolidone) and three shapes (sphere, wire and plate) at 200 and 1000 µg/L concentrations. The result from lettuce in hydroponics showed that spherical silver or gold nanoparticles with both coatings did not affect biomass significantly, but both of silver and gold nanoparticles at 1000 µg/L slightly reduced the biomass compared to the control lettuce. The effect on root leakage was similar, but spherical silver nanoparticles had slightly higher damage due to root leakage than gold nanoparticles at the same concentration. The lettuce treated to citrate-coated gold nanoparticles significantly reduced chlorophyll content compared to citrate-coated silver nanoparticles. Secondly, when it came to the surface coating, the plant exposed to 1000 µg/L spherical citrate- coated silver or gold nanoparticles had higher root leakage compared to PVP-coated nanoparticles. Both of 1000 µg/L spherical citrate-coated silver nanoparticles and gold nanoparticles significantly reduced chlorophyll content compared to PVP-coated nanoparticles. Thirdly, for different shapes of PVP-coated silver nanoparticles, the plant exposed to plate shaped and sphere shaped silver nanoparticles had significantly lower biomass compared to the wire shaped silver nanoparticles. The plant exposed to spherical silver nanoparticles had the lowest chlorophyll content between plate shaped and wire shaped silver nanoparticles. In addition, the result from lettuce in sand medium showed that the biomass production and the root leakage showed no significant difference between spherical citrate-coated, spherical PVP-coated, and silver ions at 200 µg/L. In conclusion, different nanoparticles affected different physiological processes of plants differently.

With the recent development of nanotechnology, there has been increased production of engineered nanomaterials but limited containment strategies, resulting in inevitable release of a large amount of engineered nanoparticles (ENPs) in the environment. Many ENPs have potential adverse impacts on the environment, and one of the most commonly used ENPs, silver nanoparticle (AgNP), has attracted increased global concern. The current study focused on phytotoxicity of AgNPs to a model plant, Arabidopsis thaliana. Silver nanoparticles were introduced into the growth medium for the wild type A. thaliana plants and root uptake and translocation of AgNPs were examined in hydroponic growth condition. We also conducted growth stage based phenotypic analysis by growing A. thaliana throughout its life cycle in soil. The result indicated that: (1) wild type seeds germination was not affected by either AgNPs or their dissolved Ag+ ions; (2) AgNPs exposure resulted in a concentration- and size- dependent inhibition effect to the root elongation; (3) confocal and electron microscopy indicated that AgNPs could be taken up by seedling roots, yet most of AgNPs attached to the surface of seedling root cap; (4) AgNPs and their dissolved Ag+ ions at tested concentrations had little influence on the vegetative growth of A. thaliana, but they accelerated the floral development; and (5) the effect on the floral development stage reduced the quality of second-generation (F1) seeds, as indicated by their lower germination rate. In conclusion, AgNPs displayed both acute and chronic phytotoxicity to A. thaliana.

The most common type of adverse events in healthcare in Canada reported by the Canadian Institute for Health Information (CIHI) are nosocomial infections. Amongst nosocomial infections, implant associated infections have been reported to be most common. Despite having the implantation surgeries carefully performed, a small, but still considerable number of devices gets colonized by bacteria resulting in implant associated infections and/or surgical site infections. The patients are then started on high dose antibiotics, which if ineffective, is followed by reimplantation surgeries that leads to long hospital stays and detrimental effects in their lives. Due to this, an alternative to antibiotics is required which could prevent and/or treat bacterial colonization on implants. The main objective of this thesis was to demonstrate the effectiveness of an antimicrobial based CLKRS peptide capped silver nanoparticle coating on a metallic and polymeric based biomaterial used in various implantable medical devices. The CLKRS peptide capped silver nanoparticle formulation was specifically engineered and tested for its antibacterial and antibiofilm properties. Silver nanoparticles were synthesised by photochemical reduction of silver ions upon photocleavage of the photoinitiator I-2959. The metal nanostructure surfaces were protected with the CLKRS peptide and tested on planktonic and biofilms of P. aeruginosa, S. aureus and S. epidermidis. The bacterial quantification was done by survival colony counting. The cytotoxicity of the silver nanoparticle formulation was also tested on human dermal fibroblast, mouse bone marrow derived macrophages, and human epithelial cells by cell proliferation assay. Results show the formation of a nanometric layer of nanosilver on the surface of the material inhibiting the growth of bacteria and eradicating pre-existing biofilms with no significant cell toxicity suggesting the prepared formulation could be a useful tool in preventing and controlling infections on implants during surgery and post implantation. This technology thus could serve as an alternative therapy for surgical site infections and/or implant associated infections.

[No abstract submitted] / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate