Physical Sciences and Mathematics Commons^™

Synthesis Of A Bifunctional Heterogeneous Catalyst For The Conversion Of Lignocellulosic Biomass Into Precursors For Alternative Fuels And Fine Chemicals, Matthew David Dembo

Masters Theses

The overall goal of the research described here is to develop synthetic routes to bifunctional reagents that can be tethered into silicate matrices derived from the tin functionalized cube, Si₈O₂₀(SnMe₃)₈. The critical functional group required for reaction with cubic silicate building block is a chlorosilane, and we additionally wish to incorporate both acid and ionic liquid groups. Once in hand, a crosslinking metathesis reaction will incorporate these reagents into porous silicate matrices derived from the Si₈O₂₀ cube, creating platforms with both acid and ionic liquid groups tethered to their …

Time Dependent Density-Functional Theory - Linear Response, Bryan Edman Sundahl

Masters Theses

The formal derivation of the linear response of time-dependent density-functional theory as shown by E. K. U. Gross is presented. The transformation of formal theory to the working linear response equations in the form of Casida's eigenvalue equation is demonstrated, and the results are applied to small monatomic, diatomic and triatomic systems. The application of different operators to the perturbed density is discussed, with the most attention being given to the dynamic polarizabilities. The dynamic polarizabilities and excitation spectra for N₂ [nitrogen gas] are then analyzed. The first excitation energy is noted to be in line with Koopmans' theorem. …

Demonstration Of A Targeted Proteome Characterization Approach For Examining Specific Metabolic Pathways In Complex Bacterial Systems, Adam Justin Martin

Masters Theses

Multiple Reaction Monitoring (MRM) is a powerful tandem mass spectrometry (MS/MS) tool frequently implemented in proteomic studies to provide targeted analysis of proteins and peptides. The selectivity that MRM delivers is so strong that it provides the quadrupole mass spectrometers (QQQ), on which it is commonly employed, with pertinence to proteomic studies that they would otherwise lack for their relatively low resolution. Additionally, this increased level of selectivity is sufficient enough to supplant complicated fractionation techniques, additional dimensions of chromatography, and 24 hour long MS/MS experiments in simplistic biological samples. But there is a deficiency of evidence to determine the …

Using Soil Organic Matter As An Iron Chelate To Enhance The Efficiency Of Modified Fenton Oxidition Of Diesel Fuel In Arctic Soils, Mary K. Sherwood

Masters Theses

Laboratory experiments were conducted to investigate the use of modified fenton chemistry on the treatment of three soils from the Canadian arctic, all with abundant soil organic matter, iron and manganese oxides, and diesel fuel contamination. The purpose of these studies was to (I) to assess modified fenton chemistry as a treatment option for petroleum-contaminated arctic soils, and (2) to evaluate the impact of soil organic matter on the modified fenton treatment of soils. Modified fenton treatment was compared for reactions in which ethylenediaminetetraacetate was added as a chelate vs. reactions in which the native soil organic matter was the …

Phosphatidylinositol 3,4,5–Trisphosphate Probe Synthesis And Microarray Protein Binding Studies To Investigate Multivalency And Detect Proteins Upregulated In Cancer, Benjamin Michael Smith

Masters Theses

Protein–lipid binding interactions control many processes at the cellular level. Many of these biological events between proteins and lipids are often associated with signaling pathway diseases such as cancer and diabetes. Therefore, increasing our knowledge of protein–lipid binding interactions will provide a better understanding of the signaling pathways of living systems. Pursuing this further, the phosphatidylinositol polyphosphates (PIPs) are an important family of signaling lipids that control key biological processes. Thus, the work described in this thesis was aimed at developing methods to validate these types of lipid–protein binding interactions. The goals of these projects were to synthesize the PIP …

Hindered Rotation Of Dihydrogen On Synthesized Metal Oxides, George Houston Rouvelas

Masters Theses

A MATLAB program was written to calculate the hindered rotational energies of the hydrogen and deuterium molecules interacting with an anisotropic potential, which may be thought of as a potential energy surface of a metal oxide substrate. It was found that an increase in the hindering potential of the rotation about the azimuthal angle lifted the degeneracy of the j = 1,mj [magnetic quantum number] = plus or minus 1 states. A better understanding of how the rotational states of these systems change as a function of the hindering potential can help to explain features in rotational inelastic neutron scattering …

Relative And Absolute Quantitation Of Metabolites And Lipids Using Lc/Ms/Ms On The Tsq Quantum Discovery Max, Jesse Lee Middleton

Masters Theses

Two biological systems were studied using LC/ESI/MS/MS on a triple quadrupole operated in SRM (selected reaction monitoring) scan mode. The first bacterium system is aquatic and microscopic in size known as Roseobacter. The second mammalian system is terrestrial and large in size relative to humans known as Holstein cows.

Roseobacter is a clade of marine bacteria abundant in the ocean. Roseophages are viruses that infect Roseobacter and cause viral lysis. Sulfitobacter sp. 2047 was isolated and infected with Roseophages, and the fold change in the metabolic pool relative to a control was studied at discrete time points. The absolute concentration …

Adsorption Of Antimony By Birnessite And The Impact Of Antimony On The Electrostatic Surface Properties Of Variable-Charge Soil Minerals, Kalyn Alaine Vergeer

Masters Theses

Antimony (Sb) is a toxin that can be found in high concentrations in the soil due to anthropogenic sources. Antimony exists in soil as Sb(V) in the monovalent antimonate hydroxyanion. The adsorption mechanisms of Sb(V) are not well-characterized. The objective of this study was to further elucidate Sb(V) adsorption mechanisms by examining the impact of adsorption on surface charging characteristics of gibbsite, goethite, birnessite, and kaolinite. Also examined was Sb(V), SO₄ [sulfate], and PO₄ [phosphate] adsorption by birnessite. Electrophoretic mobility and potentiometric titrations were employed to examine the ζ-potential [zeta-potential] and net proton surface charge density as a …

Study Of The Insulin Mimetic Sodium Orthovanadate In Glucosamine Induced Insulin Resistnace In Primary Rat Hepatocytes, Kalan Mcpherson

Masters Theses

Insulin resistance and type II diabetes is a disease state characterized by a lack of sensitivity of insulin to provoke a proper response in insulin sensitive tissues. Currently, we utilize glucosamine to increase flux through the Hexosamine Biosynthetic Pathway (HBP) to induce an insulin resistance like state in primary rat hepatocytes. We tested the effectiveness of the insulin mimetic sodium orthovanadate to determine if it could elicit an insulin-like response under these conditions. Mixed results were obtained on the effectiveness of vanadate as an insulin mimetic in this insulin resistant model.

Part I: Increased Leaching Of Arsenic, Selenium, Molybdenum, And Vanadium From High Calcium Coal Ash Containing Trona Reaction Products. Part Ii: Using Agricultural Byproduct Rice Hull As Biosorbent To Remove And Recover Metal Ions In Water, Yongbo Dan

Masters Theses

"Part I. The trona is being injected to control SO_x emission from coal-fired power plants. The results showed that trona ash leached significantly more As, Se, Mo, and V than the control fly ash did, especially under the natural pH condition. In addition, trona ash had a significantly greater soluble fraction than the control ash. Further investigation indicated that greater amounts of the studied anionic elements in the trona ash were associated with the soluble, trona reaction products. Moreover, the insoluble fraction of the trona ash lost its capability to adsorb these elements under the natural pH condition. The …

Crystal Structures Of Metal Sulfonates, Jon Lyle Obrecht

Masters Theses

Designing new materials with predictable chemical and physical properties has long been a goal of synthetic chemists. The functional properties of molecular compounds are intimately tied to the underlying chemical framework. In addition to atom selection and chemical connectivity, the spatial organization of the molecules often contributes to the function of materials. Because crystals are constructed of periodic arrays of components (i.e. atoms or molecules) with structures easily assessed via X-ray diffraction, crystalline materials offer ideal candidates to explore the relationship of component selection and crystal packing to material property.

One such property that has been extensively examined by …

Comparative Evaluation Of N-Acetylcysteine And N-Acetylcysteine Amide In Acetaminophen-Induced Oxidative Stress, Ahdab Naeem Khayyat

Masters Theses

"Acetaminophen (APAP) is the most widely used pharmaceutical analgesic-antipyretic agent in the world, but its toxicity is a common cause of drug-induced hepatotoxicity. With APAP toxicity, cellular glutathione (GSH) is depleted. This results in the availability of N-acetyl-p-benzoquinone imine (NAPQI), is a toxic metabolite of APAP that binds to cellular macromolecules, which leads to cell necrosis. N-acetyl cysteine (NAC), a GSH precursor, is the only approved antidote for an acetaminophen overdose. It is a negatively charged molecule that diminishes its penetration into the cells, thereby requiring fairly high doses that increase the severity of side effects. In addition, oral and …

Role Of Nicotine In Oxidative Stress, Rakesh Kacham

Masters Theses

"Nicotine, a major alkaloid, is present in tobacco products as well as in smaller amounts in potatoes, tomatoes, and eggplants. Although it is the addictive compound in cigarettes, nicotine is believed to play a protective role in neurodegenerative disorders such as Parkinson's disease. Researchers have found that the short-term administration of nicotine may help improve the memory process by reducing oxidative stress in the brain. Our studies have shown that, by blocking Fenton's reaction, nicotine is able to inhibit free radical generation, so this research has focused on the antioxidant properties of nicotine. The cell lines of the alveoli, blood …

Chemical Transformations Of Arylsulfonamide Molecular Crystals, Rajan Giri

Masters Theses

The pursuit of chemical specificity and efficiency of chemical reaction in molecular crystals has attracted considerable attention over the last decade. The successful control of molecular alignment prior to such transformations continues to provide opportunities for near quantitative yields of new materials. This thesis reports the predictable self-assembly of aryl sulfonamide materials constructed from cinnamic acid and phenylpentadienoic acid fragments capable of forming supramolecular dimers that undergo unique photocyclization reactions. Use of racemic and enantiopure single-component building-blocks provides access to enantiocontrolled [2+2] photodimerized products.

Solid-state reaction precursors were prepared using conventional solution-based synthetic organic techniques. Component chirality (racemic or homochiral) …

Determination Of Structural Stabilities Of Metal-Free Porphyrin Cytochrome C, Zinc Cytochrome C, And Cobalt Cytochrome C, Usha K. Tottempudi

Masters Theses

No abstract provided.

Studies Of The Structural Boundaries Of Solid-State Photodimerization Reactions Via Isocoumarins And Heteromeric Assemblies, Mihiri S. Weerasinghe

Masters Theses

The study of molecules in crystals has gained considerable attention in the field of structural chemistry. Much interest has focused on the use of molecular crystals for the construction of materials with specific functional properties. Because the design of such materials requires a critical understanding of intermolecular interactions, use of the building-block approach continues to offer an important strategy to multimolecular frameworks. Though the use of template and metal-ligand interactions has provided successful opportunities to organize chemical reactions in solids, these methods require secondary molecules and are limited to achiral starting materials. As such, exploring chiral synthesis with simplified precursors …

From Half-Rotaxanes To Poly-Rotaxane Architectures, Heather Renee Schoonover

Masters Theses

The host-guest abilities of macrocyclic compounds made them important players in the field of supramolecular chemistry, especially those studying mechanical bonds. Rotaxanes and catenanes are among the most well-known examples of mechanically interlocked molecules. Our approach in the synthesis of poly-rotaxane systems involves the preparation of pseudorotaxanes with donor capabilities and then use metallic centers to assemble the poly-rotaxane architectures.

A pyridine-based half-rotaxane has been synthesized and the subsequent solution studies revealed a large association constant. ¹H-NMR studies show that these interlocked species exhibit a slow exchange on the NMR timescale. Using the single point method and VT-NMR several …

The Effect Of Electrochemical Modification On The Surface Topography And Chemical Make-Up Of Strontium Titanate, Kelly J. Harmon

Masters Theses

Previous research into the oxidation and reduction of strontium titanate and the changes that result from this has been carried out. The oxidation and reduction of strontium titanate at high temperatures and high pressures has been investigated for the effect that it has upon the surface topography of strontium titanate and the chemical makeup of the strontium titanate. Research into the electrochemical oxidation of perovskites, similar in structure to that of strontium titanate, have even provided evidence pointing to the identity of the oxygen species being incorporated into the strontium titanate.

This research seeks to investigate what changes occur to …

The Effects Of Chemical Treatment And Light Exposure On Pah Concentrations In Biochar, Fathima Nadheesha Muhammed Khalid

Masters Theses

A series of experiments quantifying extractable polycyclic aromatic hydrocarbons (PAHs) in biochar before and after various treatments were conducted. The analytical approach included solvent extraction of PAHs with toluene, further isolation and column cleanup before gas chromatography mass spectroscopy (GC-MS) analysis. The treatment methods include exposing biochar samples to sunlight and UV radiation with and without additives and reacting with hydrogen peroxide.

Two biochar samples from the Eastern Illinois University bench-type gasifier and commercial biochar were analyzed. Analyzing of three biochar types revealed that plant biochar has lower total PAH concentration than wood (W) biochar or wood and plant (giant …