Physical Sciences and Mathematics Commons^™

Unprecedented Ractivity Of 1-Aza-2-Azoniaallene Salts: New Methodologies And Mechanistic Studies For The Formation Of Diazenium Salts And Tetrahydropyridazines, Nezar Al-Bataineh

Graduate College Dissertations and Theses

This thesis describes the research conducted towards the overall goal of developing new synthetic organic methods to facilitate the synthesis of structurally complex nitrogen-containing polycyclic compounds. More specifically, I will describe the diverse reactivity of 1-aza-2-azoniaallene systems to make polycyclic diazenium salts and tetrahydropyridazine rings. I will also describe mechanistic studies undertaken to better understand this reactivity.

The Brewer research group has discovered that hydrazones undergo an oxidation reaction with chlorodimethylsulfonium chloride to afford -chloroazo compounds, which react intramolecularly with pendent alkene units to give bicyclic ring fused and bridged diazenium salts. My work includes a mechanistic study to understand …

A Study Of The Physicochemical Properties Of Dense And Mesoporous Silica Nanoparticles That Impact Protein Adsorption From Biological Fluids, Alden Michael Clemments

Graduate College Dissertations and Theses

At the intersection of materials chemistry and biology, biomaterials have been successfully employed in an array of medical applications. From diagnostic tools to targeted drug delivery, the modular physical and chemical properties of these materials provide numerous applications. For example, porous nanoparticles have been widely integrated as vehicles to carry chemotherapeutics to localized tumor sites. By encapsulating these cytotoxic compounds within a porous framework, the commonly associated adverse side effects of conventional chemotherapeutics, such as Doxorubicin, have been greatly reduced. One such material, mesoporous silica, has received widespread attention due to its excellent biocompatibility, high surface area to mass ratio, …

Investigations Into Carbon Nanotube And Natural Product Synthesis., Geoffrey Giampa

Graduate College Dissertations and Theses

This dissertation describes research into the synthesis of carbon nanotubes using traditional organic synthetic methods, as well as work on the fragmentation of β-hydroxy-α-diazoesters with a γ-hetero group and applications of their reactivity towards natural product synthesis.

Carbon nanotubes are unique structures that can exhibit different electronic properties based on their chiral vector, and are a potential future source of semiconductors. Current methods of synthesis are unable to be adapted to commercial synthesis, providing the opportunity for the application of organic synthetic methods to generate them more uniformly and on a larger scale.

The generation of tethered aldehyde ynoates and …

The Role Of Green Leafy Plants In Atmospheric Chemistry: Volatile Emissions And Secondary Organic Aerosol, Rebecca Harvey

Graduate College Dissertations and Theses

Aerosols play important roles in atmospheric and environmental processes. Not only do they impact human health, they also affect visibility and climate. Despite recent advances made to under their sources and fate, there remains a limited understanding of the mechanisms that lead to the formation of aerosols and their ultimate fate in the atmosphere. These knowledge gaps provide the crux of the research reported herein, which has focused on identifying novel sources of atmospheric aerosol, characterizing its physical and optical properties, and rationalizing these properties using an in-depth knowledge of the molecular level mechanisms that led to its formation.

Upon …

A Nanoparticle/Enzyme System For The Simultaneous Detection And Decontamination Of Organophosphates, Brendon Mark Miller

Graduate College Dissertations and Theses

The need for a direct visual response system for the detection of organophosphorus compounds stems from the continued threat and use of these toxic agents in military and terrorist conflicts. The development of an enzyme-inhibitor triggered release system allows for direct visual detection with high specificity. Mesoporous silica nanoparticles (MSNs) have physical features that make them attractive as scaffolds for the construction of these systems, such as pore diameters (20-500 Á) that can be synthetically controlled, large surface areas (300-1500 m2g-1), large pore volumes, chemical inertness, stability at elevated temperatures, and surfaces that can be easily functionalized. In our studies, …

Homology Modeling And Molecular Docking Of Antagonists To Class B G-Protein Coupled Receptor Pituitary Adenylate Cyclase Type 1 (Pac1r), Suzanne Louise Stanton

Graduate College Dissertations and Theses

Recent studies have identified the Class B g-protein coupled receptor (GPCR) pituitary adenylate cyclase activating polypeptide type 1 (PAC1R) as a key component in physiological stress management. Over-activity of neurological stress response systems due to prolonged or extreme exposure to traumatic events has led researchers to investigate PAC1R inhibition as a possible treatment for anxiety disorders such as post-traumatic stress disorder (PTSD). In 2008, Beebe and coworkers identified two such small molecule hydrazide antagonists and a general pharmacaphore for PAC1R inhibition. However, a relative dearth of information about Class B GPCRs in general, and PAC1R in specific, has significantly hindered …

Excitonic States In Crystalline Organic Semiconductors: A Condensed Matter Approach, Lane Wright Manning

Graduate College Dissertations and Theses

In this work, a new condensed matter approach to the study of excitons based on crystalline thin films of the organic molecule phthalocyanine is introduced. The premise is inspired by a wealth of studies in inorganic semiconductor ternary alloys (such as AlGaN, InGaN, SiGe) where tuning compositional disorder can result in exciton localization by alloy potential fluctuations. Comprehensive absorption, luminescence, linear dichroism and electron radiative lifetime studies were performed on both pure and alloy samples of metal-free octabutoxy-phthalocyanine and transition metal octabutoxy-phthalocyanines, where the metal is Mn, Co, Ni, and Cu. Varying the ratios of the metal to metal-free phthalocyanines …

Establishing Chemical Mechanisms And Estimating Phase State Of Secondary Organic Aerosol From Atmospherically Relevant Organic Precursors, Shashank Jain

Graduate College Dissertations and Theses

Organic aerosol (OA) is a ubiquitous component of atmospheric particulate that influences both human health and global climate. A large fraction of OA is secondary in nature (SOA), being produced by oxidation of volatile organic compounds (VOCs) emitted by biogenic and anthropogenic sources. Despite the integral role of SOA in atmospheric processes, there remains a limited scientific understanding of the chemical and physical changes induced in SOA as it ages in the atmosphere. This thesis describes work done to increase the knowledge of processes and properties of atmospherically relevant SOA.

In the work presented in this thesis, I have worked …

Investigating The Influence Of Gold Nanoparticles On The Photocatalytic And Catalytic Reactivity Of Porous Tungsten Oxide Microparticles, Daniel P. Depuccio

Graduate College Dissertations and Theses

Tungsten oxide (WO3) is a semiconducting transition metal oxide with interesting electronic, structural, and chemical properties that have been exploited in applications including catalysis, gas sensing, electrochromic displays, and solar energy conversion. Nanocrystalline WO3 can absorb visible light to catalyze heterogeneous photooxidation reactions. Also, the acidity of the WO3 surface makes this oxide a good thermal catalyst in the dehydration of alcohols to various industrially relevant chemicals. This dissertation explores the photocatalytic and thermal catalytic reactivity of nanocrystalline porous WO3 microparticles. Furthermore, investigations into the changes in WO3 reactivity are carried out after modifying the porous WO3 particles with gold …

Second Coordination Sphere Of Heme In Mycobacterium Tuberculosis Mhud, And The Mechanism Of Heme Degradation, Amanda Graves

Graduate College Dissertations and Theses

MhuD is a heme degrading enzyme from Mycobacterium tuberculosis that catalyzes both monooxygenation and dioxygenation leading to novel chromophores, mycobilins. The X-ray crystal structure of heme-bound, cyanide-inhibited MhuD displays a ruffled heme substrate where pyrrole rings are rotated around the Fe-N bonds, distorting the heme. The electronic structure of the heme in heme-bound, cyanide-inhibited MhuD (MhuD-heme-CN) is characterized here to provide insight into the mechanism of heme degradation by MhuD. Analysis of nuclear magnetic resonance (NMR) and magnetic circular dichroism (MCD) data for MhuD-heme-CN leads to the conclusion that the ground, (dxz,yz)4(dxy)1 electron configuration (2B2g state) and excited (dxy)2(dxz,yz)3 electron …

Oxygen-Sensitive Luminophores: A Survey Of The Literature And Efforts Toward A Novel Porphyrin-Pillared Zirconium Phosphonate, Joseph Wright

Graduate College Dissertations and Theses

Measurement and mapping of the pressure distribution across the surface of a suitably scaled model is an integral step in the design of any aircraft or automobile. For this purpose, the traditional workhorses of the aeronautic and automotive industries have been pressure taps--small orifices that contain electronic pressure transducers. Unfortunately, in addition to the limited spatial resolution achievable with such devices, their technical complexity and cost constitute serious disadvantages. For more than 35 years, researchers have pursued a fundamentally different alternative: indirect measurement of pressure via oxygen-induced quenching of the luminescence emitted by certain chemical species. Porphyrin complexes of dipositive …