Physical Sciences and Mathematics Commons^™

Selective Oxidation Of Alkenes In Air Catalyzed By Mn3o4 Nanoparticles, Brojo Kishor Shachib Dhali

Dissertations and Theses

Catalytic oxidation is a process where compounds are oxidized using catalysts. Solid catalysts exhibit several advantages over homogeneous systems, such as catalyst recovery and excellent stability. Various supported transition-metal oxides (for example: CuO, ZnO, CeO2, Fe2O3 and WO3), metal nanoparticles (for example: Pd and Ru) and polyoxometalate clusters (for example: [W10O32]4-, [Mn2ZnW(ZnW9O34)2]10- and [XW12O40]n- (X = P, Si)) have been applied to selective oxidation of organic compounds, but high associated product conversion still remains a challenge. Recently, a number of materials containing Mn3O4 have been used successfully in different catalytic applications, such as degradation of phenols, reduction of nitrobenzenes, and …

Exploring The Potential Use Of Porous Silica Nanoparticles In Cest-Mri, Lydia Makotamo

Dissertations and Theses

Magnetic resonance imaging (MRI) is a widely used modality in diagnostics, treatment, and monitoring various conditions due to its ability to generate high-resolution images using non-ionizing radiation. The advent of contrast agents, which generally work by increasing the spin relaxation rate constants of water protons, has led to image enhancement. Despite the usefulness of this class of agents in diagnostic medicine, their inability to provide in-depth functional and anatomical information, coupled with their high detection limits, has led to new agents being explored.

Chemical exchange saturation transfer (CEST) presents an alternative route to generate signals via repetitive saturations transfers between …

Designing Environmentally Responsible And Highly Effective Bioorthogonally Functionalized Chiral Mri Contrast Agents, Karley Breann Maier

Dissertations and Theses

Magnetic resonance imaging (MRI) revolutionized diagnostic imaging and modernized the characterization of numerous diseases. The clinical success of MRI is in large part due to the employment of gadolinium-based contrast agents (GBCAs). Due to sensitivity limitations, GBCAs are indicated at markedly high dosages (~1 g Gd³⁺ per exam). The routine use of such large quantities of gadolinium poses significant health and environmental risks. There are growing concerns over the effects of dechelation of the metal in vivo and the possible effect of resulting gadolinium deposition. Concurrently, there is a rising awareness of gadolinium anomalies borne by GBCAs which undergo …

Selenium Probes For The Detection Of Thioredoxin Reductase Activity, Tendai Joseph Mafireyi

Dissertations and Theses

The identification and quantification of proteins and enzymatic activity in living tissues frequently requires the use of invasive procedures such as biopsy. These techniques can inhibit measurements of protein levels in real-time, and the disruption of tissue can lead to the loss of important information concerning the spatial distribution and differential activities in various cell types. The use of small organic fluorescent probes that rely on activation or accumulation within a tissue embody robust methods of detection that address these issues. This dissertation describes the design, synthesis and evaluation of fluorescent probes that can detect the enzyme thioredoxin reductase (TrxR). …

Mechanistic Investigation Of Neuropeptide S-Nitrosylation By Nitric Oxide Moieties: A Kinetic And Thermodynamic Approach, Vusumuzi Leroy Sibanda

Dissertations and Theses

This dissertation focuses on providing quantitative insights regarding kinetic, thermodynamic and mechanistic parameters of neuropeptide S-nitrosylation by nitrous acid (HNO₂), peroxynitrite (ONOO^-) and S-nitroso-N-acetyl-D,L-penicillamine (SNAP) to produce S-nitrosothiols (SNOs). Peptide thiol stability and the formation of SNOs from neuropeptides; arginine vasopressin (AVP), somatostatin-14 (SST-14) and urotensin II (U-II) was studied. Investigations into the effects of temperature, copper chelators and pH on peptide thiol autoxidation show that AVP, SST-14 and U-II thiols have half-lives of 30, 44 and 28.2 mins respectively at physiologically relevant temperature and pH in the absence of metal chelators. Target peptide thiols were …

The Development And Application Of Instrumental Methods For The Identification Of Materials And Processes Used In The Manufacture Of Orotone, Hand-Colored Orotone, And Silvertone Photographs, Ivanny Jeannette Jácome-Valladares

Dissertations and Theses

Orotone photographs are positive photographic images on glass with a gold-colored metallic coating or backing. Although the materials and process used in the production of orotones have been previously documented, there is limited published scientific research on the subject. This study focused on expanding those published works by analyzing a greater number of photographs, including eleven orotones, four hand-colored orotones, two silvertones, and one uncoated orotone. The photographs, dating from the early to mid-20^th century, were from the University of Washington (UW) Libraries' collection, except for one orotone that was from the Portland Art Museum.

X-ray Fluorescence (XRF) spectroscopy, …

Tellurorhodamine Photocatalysts In Aerobic Oxidation Reactions: Development Of Synthetic Methods And Reaction Mechanisms, Irving D. Rettig

Dissertations and Theses

Aerobic oxidation photocatalysis involves the use of oxygen as an oxidant species, coupled to a light driven catalyst to achieve useful chemical transformations. Catalytic aerobic oxidation reactions can be defined as either oxidase-like, in which O₂ acts as an electron donor/acceptor but is not incorporated into the reaction products, or oxygenase-like where O₂ acts as an electron donor/acceptor and is incorporated into the reaction products. A multitude of inorganic catalysts have been developed that can achieve a wide scope of oxidase-like or oxygenase-like reactivity, however, it is rare for a catalyst to be capable of both. We report …

Investigations Into Size And Surface Control Of Silicon Nanocrystals For Improved Optical Properties, James Donald Barnes

Dissertations and Theses

The discovery of visible photoluminescence (PL) from nanocrystalline porous silicon in 1990 led to extensive research into the mechanisms of the emergent properties, and optimization of these properties, for use in applications. The widespread use of silicon nanoparticles (Si NPs) in commercial applications is currently limited by three main factors: 1) poor radiative recombination efficiency of the interband transition, 2) instability of the interband photoluminescence, and 3) a lack of scalable methods for producing Si NPs that are both highly crystalline and size monodisperse.

To address these limitations, this dissertation correlates changes in the photoluminescence properties of hydrogen passivated silicon …

Steady-State Transmembrane Water Exchange In Proliferating Cultures Of Saccharomyces Cerevisiae, Joseph O'Malley Armstrong

Dissertations and Theses

Cellular water exchange is often considered in terms of a change in volume, where a net flux of water moves across the cell membrane due to a change in osmotic pressure. Osmotic pressure can cause a cell to shrink or swell, however, rapid water exchange persists across the membrane even when the volume of the cell is constant. Steady-state transmembrane water exchange describes the exchange of water across the cell membranes which results in no net change in cell volume. This exchange is astonishingly rapid; the entire pool of intracellular water of a Saccharomyces cerevisiae cell may exchange 2-5 times …

Chemical Characterization Of Toxicologically Relevant Molecules In Cannabis Concentrates And Vaporizer Aerosols, Jiries Meehan-Atrash

Dissertations and Theses

Consumption of cannabis concentrates using the relatively novel non-combustion methods dabbing and vaping has steadily grown in popularity as cannabis legalization in North America has allowed increased access to sophisticated cannabis products and technology. In order to assess the safety of these products, it is necessary to gain a chemical understanding of the decomposition reactions that occur when the active ingredients are heated in the conditions seen when dabbing or vaping. This dissertation contains a manuscript that details efforts to structurally characterize a toxic cannabis concentrate adulterant, and three manuscripts that studied the chemical decomposition of the two primary cannabis …

Complex Fluid Dynamics: Chemo-Hydrodynamics Driven By Autocatalytic Reaction Fronts, Matthew Walter Eskew

Dissertations and Theses

Chemo-hydrodynamics generated from reaction-diffusion-convection processes of autocatalytic chemical systems are extensively studied for their applications in modeling complex systems. Compared to the more extensively studied autocatalytic systems, chlorite-tetrathionate and chlorite-trithionate, the chlorite-thiourea systems is relatively unexplored. Compared to the two previous systems, chlorite-thiourea has more straightforward chemical kinetics. To narrow the gap between chlorite-thiourea and the other systems a combination of experimental study and numerical simulation were employed to quantify this system.

Compared to established literature, experiments were performed at five orders of magnitude lower concentration of indicator, minimizing confounding effects of indicator on hydrodynamic motion. To accurately image the …

Thermodynamics Of Ligand Binding And Global Structural Stability Of Human Serum Albumin, Matthew Walter Eskew

Dissertations and Theses

Protein structure is integral to its function. For the past 70 years differential scanning calorimetry has been used to measure protein structural stability. More recently it has been used to study macromolecular interactions. Interactions between proteins and ligands can manifest on differential scanning calorimetry melting curves or thermograms. Utilizing differential scanning calorimetry thermograms to detect or diagnose diseases has been a major goal in disease diagnostics. However, correlating specific ligand-protein interactions, as manifested in a thermogram, with a disease-specific plasma thermogram, has proven elusive.

Modified human serum albumin was utilized to develop a process to capture and retrieve ligands from …

Comparison Of Calculated Normal Mode Molecular Vibrations With Experimental Gas-Phase Infrared Spectroscopy, Anila Renis Sutar

Dissertations and Theses

Computational vibrational spectroscopy serves as an important tool in the interpretation of experimental infrared (IR) spectra. Analysis of computational results provides a perspective over broader wavelength ranges and at higher precision. Although there are issues regarding accuracy, this can be approximated by using a scaling factor. High-resolution gas-phase FTIR spectroscopy at a resolution of 0.125 cm^-1 can partially resolve rovibrational transitions in the P, Q, and R bands and therefore identify fundamental frequencies with approximately 1 cm^-1 precision.

This research has compared high-resolution gas-phase FTIR absorption peaks to calculated vibrational frequencies. In the calculation of normal mode frequencies, …