Physical Sciences and Mathematics Commons^™

Isolation, Characterization And Synthesis Of Asthma Inducing Fungal Glycolipid And Analytical Method Development For Novel Antimicrobial Peptide Mimics, Vinod Chaudhary

Theses and Dissertations

NKT cells are an important part of human immune system and recognize a specific set of antigens called glycolipids. Only a handful of "natural" NKT cell antigens are known till date. Although NKT cells play a protective role against pathogenic organisms, imbalances in NKT cell functions are implicated in many diseases including asthma. Allergic asthma, a Th2 driven inflammation of airways, is primarily caused by inhalation of environmental allergens. In the last decade, inhaled allergen Aspergillus fumigatus has been under scrutiny for the presence of NKT cell antigens that might trigger asthma. We successfully isolated, characterized and synthesized a "natural" …

Synthesis And Immunological Evaluation Of Type I, Type Ii, And Gamma Delta Nkt Cell Antigens, Brian L. Anderson

Theses and Dissertations

The purpose of the immune system is to protect our bodies from infection. One way it accomplishes this task is through the presentation of foreign pathogens to NKT cells. After an antigen is presented to the T cell receptor, activated NKT cells quickly release soluble chemical signals, termed chemokines and cytokines, that modulate the response of the immune system. Due to the immunological relevance of NKT cell activation, we developed and synthesised non-natural analogs of immunostimulatory type I, II, and gamma delta NKT cell antigens. The immunological evaluations of these analogs resulted in identification of sulfatide as a gamma delta …

Binding Energies And Solvation Of Organic Molecular Ions, Reactions Of Transition Metal Ions With, And Plasma Discharge Ionization Of Molecular Clusters, Isaac Kwame Attah

Theses and Dissertations

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and …

Probing Bonding And Dynamics At Heterogeneous Adsorbate/Graphene Interfaces, Eric Charles Mattson

Theses and Dissertations

Graphene-based materials are becoming an astoundingly promising choice for many relevant technological and environmental applications. Deriving graphene from the reduction of graphene oxide (GO) is becoming a popular and inexpensive route toward the synthesis of these materials. While the desired product from GO reduction is pristine graphene, defects and residual oxygen functional groups inherited from the parent GO render reduced graphene oxide (RGO) distinct from graphene. In this work, the structure and bonding for GO and RGO is investigated to the end of a working understanding of the composition and properties of these materials. In situ selected area electron diffraction …

Towards The Use Of Time-Resolved X-Ray Crystallography In Mechanistic Studies Of Cytochrome C Nitrite Reductase From Shewanella Oneidensis, Matthew David Youngblut

Theses and Dissertations

A high-yield expression and purification of Shewanella oneidensis cytochrome c nitrite reductase (ccNiR), and its characterization by a variety of methods, notably Laue crystallography, is reported. A key component of the expression system is an artificial ccNiR gene in which the N-terminal signal peptide from the highly expressed S. oneidensis protein "Small Tetra-heme c" replaces the wild-type signal peptide. This gene, inserted into the plasmid pHSG298 and expressed in S. oneidensis TSP-C strain, generated approximately 20 mg crude ccNiR/L culture, compared with 0.5-1 mg/L for untransformed cells. Purified ccNiR exhibited nitrite and hydroxylamine reductase activities comparable to those of E. …

An Optical-Fiber Based Sensor Array For The Simultaneous Analysis Of Zinc And Copper In Aqueous Environments, Steven Kopitzke

Theses and Dissertations

Copper and zinc are elements commonly used in industrial applications, with many of these processes using these elements in aqueous environments. Before the solutions can be discharged into civil or native waterways, waste treatment processes must be undertaken to ensure compliance with federal, state and local guidelines restricting the concentration of ions discharged in solution. While there are methods of analysis currently available to monitor these solutions, each method has disadvantages, be it that they are cost prohibitive, inaccurate, and/or time-consuming. In this work, a new optical fiber-based platform capable of providing fast and accurate results when performing solution analysis …

Functional Organic Nanomaterials, Ryan R. Kohlmeyer

Theses and Dissertations

π-Conjugated polymers have a wide range of applications such as photovoltaics, light-emitting diodes, and sensors. To gain a better understanding of these systems, monodisperse oligomers can be used as a more simplistic model to generate predictive structural and physical properties of corresponding polymers. A divergent/convergent synthetic approach to synthesis of monodisperse π-conjugated oligomers has been developed. These well-defined, thiophene-containing molecular building blocks have been successfully coupled to a ferrocene hinge, which has been found to be highly efficient in the transport of gold atoms using a gold scanning tunneling microscopy tip.

Carbon nanotubes (CNTs) represent a rare class of materials, …

Characterization Of The Distribution, Abundance, And Fate Of Metals In Sediment, April Grant

Theses and Dissertations

This research describes the mobility of heavy metals in river sediment through characterization of metal-sediment association by a sequential extraction procedure. The most abundant isotopes of As, Cd, Cu, Cr, Pb and Zn were measured by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in four sediment extraction phases: a) exchangeable, b) carbonate-bound, c) metal-oxide-bound, and d) organic-bound. The measured concentrations were compared to the Wisconsin Department of Natural Resources' "Sediment Quality Guidelines" to determine whether the metals were present at toxic levels. Two reference techniques, Potentiometric Stripping Analysis and Graphite Furnace Atomic Absorption Spectroscopy, were used to validate the concentrations of metals …

Infrared Light Induced Bending Of Liquid Crystalline Elastomer Composite-Silicone Bilayer Films, Maika Moua

Theses and Dissertations

This research centers on infrared (IR) light-induced bending of liquid crystalline elastomers (LCE) composite-silicone bilayer films. Two new developments are presented in this thesis. First, the reversible infrared (IR) induced bending of 0.1% (w/w) single walled nanotube (SWNT)-LCE/silicone bilayer films were successfully prepared and used for fabrication of functioning devices such as folding, grabbing, and crawling structures. Second, the use of adding a filler (absorbs specific wavelength range), such as Dye 1002, into the LCE matrix achieved wavelength selectivity in LCE systems. The 0.2% (wt/wt) Dye 1002-LCE/silicone bilayer films demonstrated bending under a 980 nm laser source but no bending …

High-Throughput Approaches For The Assessment Of Factors Influencing Bioavailability Of Small Molecules In Pre-Clinical Drug Development, Megan Marie Mccallum

Theses and Dissertations

A bioactive molecule must pass many hurdles to be designated as a "good" pharmaceutical lead or hit compound. It should have a significant activity, selectivity, bioavailability, and metabolic half-life. Many factors have been identified that influence the free drug concentration or bioavailability of orally administered drugs in the earliest development stages. In vitro pre-clinical assays have been developed to measure these parameters. The small molecule properties that are investigated here include aqueous solubility, permeability, reactivity (electrophilicity), small molecule-protein binding, and displacement of protein-bound molecules (drug-drug interactions). The development of rapid and miniaturized assays to quantify these factors is presented herein. …

Methods In Metallomics, Proteomics, And Toxicology: Development And Applications Of Laser Ablation Inductively Coupled Plasma Mass Spectrometry And Native Sds-Page, William John Wobig

Theses and Dissertations

Polyacrylamide gel electrophoresis (PAGE) is a bio-analytical method used to separate proteins in solution into an array of individual bands of proteins in a gel matrix. Current PAGE methods, however, have severe limitations in simultaneously maintaining a protein's native structure and association with transition metals while providing adequate resolution. Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) provides a means to perform trace to ultra-trace level inorganic analysis of solid samples such as dried PAGE gels containing metallo-protein arrays. Current LA-ICP-MS methods involving the analysis of PAGE gels, however, have been limited in their effective use by inadequate limits of …

Anion Effects In The Extraction Of Metal Ions Into Room-Temperature Ionic Liquids (Rtils), Sarah Lynn Garvey

Theses and Dissertations

As part of a broader program directed at the development of improved approaches to the removal of actinides and heat-producing fission products from spent nuclear fuel, the fundamental aspects of the partitioning of selected metal ions between aqueous solution and various room-temperature ionic liquids (ILs) containing a neutral extractant have been investigated.

Prior work has shown that in contrast to the partitioning of alkaline earth cations into conventional solvents in the presence of a crown ether, which is known to proceed via a single pathway (i.e., neutral complex extraction), their extraction into an IL is often a complex, multi-path process …

Kinetics Of Atmospheric Reactions Of Biogenic Volatile Organic Compounds: Measurement Of The Rate Constant Ofthujone + Cl· At 296 K And Calculation Ofthe Equilibrium Constant For The Ho2ch2ch2o2· H2o Complex, Marie Coy Killian

Theses and Dissertations

Biogenic volatile organic compounds (VOCs) react with Cl and OH radicals and the resulting radicals combine with oxygen to form peroxy radicals RO2. Organic peroxy radicals can then react with NO to form NO2, a precursor of tropospheric ozone. The work presented here explored the initial reaction between Cl and thujone, a VOC emitted by Great Basin sagebrush. The rate constant for the reaction of thujone + Cl at 296 K was measured with the method of relative rates with FTIR for detection of reactants. LEDs were used to photolyze Cl2 to generate Cl in the reaction cell. Thujone was …

Formation Mechanisms And Photocatalytic Properties Of Zno-Based Nanomaterials, Natalie Herring

Theses and Dissertations

Zinc Oxide (ZnO) is one of the most extensively studied semiconductors because of its unique properties, namely, its wide band gap (3.37 eV) and high excitation binding energy (60 meV). These properties make ZnO a promising material for uses in a broad range of applications including sensors, catalysis and optoelectronic devices. The presented research covers a broad spectrum of these interesting nanomaterials, from their synthesis and characterization to their use as photocatalyts. A new synthetic approach for producing morphology controlled ZnO nanostructures was developed using microwave irradiation (MWI). The rapid decomposition of zinc acetate in the presence of a mixture …

Graphene-Based Semiconductor And Metallic Nanostructured Materials, Abdallah Zedan

Theses and Dissertations

Exciting periods of scientific research are often associated with discoveries of novel materials. Such period was brought about by the successful preparation of graphene which is a 2D allotrope of carbon with remarkable electronic, optical and mechanical properties. Functional graphene-based nanocomposites have great promise for applications in various fields such as energy conversion, opteoelectronics, solar cells, sensing, catalysis and biomedicine. Herein, microwave and laser-assisted synthetic approaches were developed for decorating graphene with various semiconductor, metallic or magnetic nanostructures of controlled size and shape. We developed a scalable microwave irradiation method for the synthesis of graphene decorated with CdSe nanocrystals of …

Facile Synthesis And Improved Pore Structure Characterization Of Mesoporous Γ-Alumina Catalyst Supports With Tunable Pore Size, Baiyu Huang

Theses and Dissertations

Mesoporous γ-alumina is the most extensively used catalysts support in a wide range of catalytic processes. The usefulness of γ-alumina relies on its favorable combination of physical, textural, thermal, and chemical properties. Pore structure properties are among the most important properties, since high surface area and large pore volume enable higher loading of active catalytic phases, while design of pore size and pore size distribution is critical to optimize pore diffusional transport and product selectivity. In addition, accurate determination of surface area (SA), pore volume (PV) and pore size distribution (PSD) of porous supports, catalysts, and nanomaterials is vital to …

Resorcinarene-Based Cavitands: From Structural Design And Synthesis To Separations Applications, Na Li

Theses and Dissertations

Resorcinarenes are cyclic tetramers that are synthesized by the condensation of resorcinol and various aldehydes. The upper and lower rims can be modified with substituents that provide specific selectivity and other chemical features. In this work, resorcinarene-based macrocyclic ligands with specific selectivities have been designed, synthesized and applied to chiral amine discrimination and transition metal ion separations.These resorcinarenes fall into two categories. In the first type, the upper rims of resorcinarenes were modified with amino acid groups, including chiral alanine groups. The lower rims were modified with --CH3, or --C11H23 groups. The structures were studied by nuclear magnetic resonance (NMR), …

Metallization Of Dna And Dna Origami Using A Pd Seeding Method, Yanli Geng

Theses and Dissertations

In this dissertation, I developed a Pd seeding method in association with electroless plating, to successfully metallize both lambda DNA and DNA origami templates on different surfaces. On mica surfaces, this method offered a fast, simple process, and the ability to obtain a relatively high yield of metallized DNA nanostructures. When using lambda DNA as the templates, I studied the effect of Pd(II) activation time on the seed height and density, and an optimal activation time between 10 and 30 min was obtained. Based on the Pd seeds formed on DNA, as well as a Pd electroless plating solution, continuous …

Structural And Photoluminescent Characterization Of Substituted A3mo4f (A = Sr, Ba, Ca; M = Al, Ga, In, Si And Ge), Robert Lenwood Green

Theses and Dissertations

In this dissertation, the structure and photoluminescent properties of A3MO4F-type materials (A = Sr, Ba, Ca; M =Al, Ga, In, Si, Ge) are studied as potential phosphors for compact fluorescent lamps (CFLs) and phosphor converted light emitting diode (pc LED) lights. Chapter 1 outlines background information of the evolution of lighting technology as well as detailing the synthesis, structural characterization and photoluminescence measurements. Chapter 2 focuses on the changes that the Sr3AlO4F structure undergoes as a result of exposure to a 5% H2/95% Ar atmosphere. High-resolution neutron powder diffraction is used to probe for minute structural changes. Chapter 3 is …

The Scope Of The Bis-Urea Macrocycle Assembly Motif, Michael F. Geer

Theses and Dissertations

From the formation of rock candy crystals, to the functionality of DNA in the cell, to the cosmic dust throughout the universe, supramolecular chemistry has a great impact and importance in the world around us. In this thesis, we explore the supramolecular interactions and self-assembly of bis¬-urea macrocyclic systems and investigate how their structure and assembly influences bulk properties and functionality. Specifically, in chapter one, we review the factors that guide, limit, and define supramolecular structures from the atomic to the centimeter scale.

In chapter two, we investigate the incorporation of benzophenone, a well known triplet sensitizer, within a bis-urea …

Renewable Bio-Based Polymers And Degradable Functional Polymers, Kejian Yao

Theses and Dissertations

In this dissertation, polymers derived from renewable bio-based resources and degradable functional polymers with stimuli-responsive properties by various polymerization techniques were investigated. The properties of these polymeric materials were characterized and discussed.

In Chapter 1, the overall background and recent development of renewable bio-based polymers as well as degradable stimuli-responsive polymers was introduced. Major research objectives of my doctoral work were described.

The first section of the dissertation, on the preparation of renewable bio-based polymers was provided from Chapter 2 to Chapter 4. In Chapter 2, the preparation of novel polymers derived from renewable gum rosin by atom transfer radical …

Thermal Infrared Imaging: Instrumentation And Method Development, Wayne O'Brien

Theses and Dissertations

A recently development thermal infrared camera system was improved by designing new components to downsize physical aspect and improve the instrument's performance. A new thermal infrared light source was developed and characterized. It is designed from a custom-made Macor backpiece that holds an alumina screw. High resistance wire is coiled around the screw. The coiled wire is covered with an alumina coating. Most light sources have a spectral emissivity similar to that of a blackbody emitter. This source has a spectral irradiance profile that is not similar to a blackbody source. Thus, the lamp has an improved efficiency in the …

Preparation And Characterization Of Palladium Catalysts, Michael J. Anderson

Theses and Dissertations

There is a critical need for improved combustion-oxidation catalysts to reduce emissions of toxic volatile organic compounds (VOCs) emitted from exhaust gas of gasoline combustion in automotive vehicles. Materials and systems currently available, such as the three way catalytic converter (TWC), have low activity below 400 °C in the catalytic process. Palladium catalysts were prepared by alternative methods including: preparation by wet impregnation or incipient wetness, drying by room temperature or air-oven, and support choice between silica and alumina. These catalysts were prepared to meet the demand for low temperature oxidation. Results indicated a 5% increase in percent dispersion of …

Programmable Polymers Preparation Optimization And Applications On Solute Templates, Yinyan He

Theses and Dissertations

Programmable polymer is a type of stimuli-responsive polymer which can keep their induced properties after removal of the stimulu, as well as programmable polymers maintain the general properties as stimuli-responsive polymers, such as recognize and respond to the stimulus. The previous reported solvent Caryl-Nimide bonds based programmable polymers (SPP-1) can freely rotate and change the carboxylic acid recognition group orientation in response to templates. Solvent templates were used in the SPP-1. One potential application for SPPs is using their recognition and memory properties for the identification and separation of mixture solutions of various analytes. In my first project, I wanted …

Polybenzimidazole Membranes With Enhanced Mechanical Properties For Extended Lifetime Electrochemical Applications, Max Molleo

Theses and Dissertations

After approximately 20 years of development, polybenzimidazole (PBI) chemistries and the concomitant manufacturing processes have evolved into commercially produced membrane electrode assemblies (MEAs). Commerical PBI MEAs can operate reliably for over two years at elevated temperatures of 120-180°C due to the physical and chemical robustness of PBI membranes. Recently, the Department of Energy has issued a target of 40,000-80,000 hours for stationary (i.e. combined heat and power, back-up power) polymer electrolyte membrane / proton exchange membrane (PEM) fuel cells. It is known through observation that over time, PBI membranes at 180°C creep in a direction perpendicular to compressive forces, thus …

Instrument And Method Development For Single-Cell Classification Using Fluorescence Imaging Multivariate Optical Computing, Joseph Swanstrom

Theses and Dissertations

Multivariate optical computing (MOC) is an all-optical approach of predictive spectroscopy that utilizes multivariate calibration and spectral pattern recognition techniques while operating in a simple filter photometer instrument, removing the need for expensive instrumentation and post-processing of spectral data. This is accomplished with specially designed interference filters called multivariate optical elements (MOEs). MOC can provide analytical solutions for applications requiring low cost, rugged, and simple to operate instrumentation for use in remote and hazardous environments such as open ocean waters. These instrument specifications are central for developing a method for classifying phytoplankton in their natural environment. Phytoplankton are photosynthetic single …

Study Of Porous, Crystalline Supramolecular Boronates, Vincenzo Michael Disantis

Theses and Dissertations

Porous materials with the ability to selectively absorb volatile organic compounds are of high interest for applications in sensing, sequestration and separations. Utilizing the covalent yet reversible boronate ester bonds between boronic acids and diols in conjunction with dative boron-nitrogen coordination bonds has allowed for the discovery of a new class of porous materials. Preliminary results show the ability to obtain porous, crystalline supramolecular boronate networks from the coordination of diamine linkers with boronate diester backbones. Further exploration of porous, crystalline supramolecular boronates has revealed the discovery of a porous crystalline coordination polymer that exhibits reversible, selective guest adsorption properties …

New Bimetallic Iridium Cluster Carbonyl Complexes, Mingwei Chen

Theses and Dissertations

Platinum group metal derived bimetallic clusters have been used as precursors to nanoscale catalysts which have been proven to be more effective than their monometallic counterparts. Iridium is a platinum group metal and its applications in catalysis continue to grow. To take advantages of synergies between mixed-metals, we modified iridium clusters with other metal ligands like tin, germanium, and group IB (gold, silver, copper) etc. and obtained a fairly large amount of new iridium derived bimetallic clusters which could be precursors to catalysts with superior properties than that available nowadays. The reaction of Ir4(CO)12 with Ph3SnOH in the presence of …

A Silylation Based Kinetic Resolution Of Secondary Alcohols And The Synthesis And Structural Characterization Of Pyridyl-Oxazolidine Compounds, Cody Ian Sheppard

Theses and Dissertations

Described herein is the first enantioselective silylation based kinetic resolution of monofunctional secondary alcohols to achieve useful levels of enantioselectivity. Using commercially available reagents, the reaction conditions were optimized and found to successfully resolve several secondary alcohols with high enantioselectivity. It was discovered that the nucleophilic isothiourea compound (-)-tetramisole, with Ph3SiCl as the silyl source, gave superior results to other nucleophilic catalysts and was capable of performing the kinetic resolution in as little as 45 minutes using mild reaction conditions. The structural and electronic characteristics of successful and less successful substrates are also discussed.

Chapter three discusses mechanistic investigations and …

Development And Figures Of Merit Of Microextraction And Ultra-Performance Liquid Chromatography For Forensic Characterization Of Dye Profiles On Trace Acrylic, Nylon, Polyester, And Cotton Textile Fibers, Scott James Hoy

Theses and Dissertations

Methodology for the microextraction of basic dyes on acrylic, acid dyes on nylon, disperse dyes on polyester, and reactive dyes, direct dyes, and indigo on cotton textile fibers is reported. Although these processes are destructive to the fiber evidence, the ability to analyze dye extracts from sub-millimeter fiber lengths of single fibers, coupled with detection limits in the hundred picogram range by ultra-performance liquid chromatography (UPLC) with both diode array detection (DAD) and tandem mass spectrometry (MS-MS) makes routine forensic characterization feasible.

Microextraction, followed by UPLC, can often distinguish similar fibers containing different, but similar, dyes with the combination of …