Physical Sciences and Mathematics Commons^™

Catalytic Activity Of Tungsten-Dioxo And Tungsten-Diimido Complexes, Kayla Denike

Graduate Theses and Dissertations

Due to the significant decline in the availability of petrochemical resources and the increasing demand for the useful olefin mixtures extracted from oil, a sustainable and efficient alternative to these materials has become vital. Fortunately, renewable biomass derived materials may serve as a sustainable solution to the limited resources problem. Molecules derived from the degradation of biomasses are highly oxygenated and highly functionalized. Developing processes to efficiently defunctionalize these oxygen-rich materials will lead to potential up-conversion to carbon chemicals. Homogeneous catalytic deoxygenation processes present an opportunity to access valuable carbon commodity chemicals from biomass derived polyols. This dissertation details the …

Formation Of Reactive Nitrogen Species During Dichloramine Decay And Their Impact On N Nitrosodimethylamine Formation Under Drinking Water Conditions, Huong Thu Pham

Graduate Theses and Dissertations

NDMA occurrence and formation pathways in drinking water systems are reviewed and NDMA yields are compared on the basis of disinfectant type, water chemistry, and precursor category. In chloramination, despite monochloramine being the predominant species between pH 7-9, evidence suggests that dichloramine is the primary species involved in NDMA formation. This is somewhat confounding as NDMA yields are maximal at pH 9, yet at pH 9 dichloramine decays faster than it forms and hence is present at trace levels; additionally, the proposed mechanism involves a spin-forbidden incorporation of dissolved oxygen as a triplet, which is presumably kinetically slow. This review …

Investigation Of Factors Influencing Recombination Versus Disproportionation Of Complex Radicals Formed By C-N Homolysis Of Breslow Type Intermediates And Related Compounds, Taylor Burnett

Graduate Theses and Dissertations

Electron rich enamines are capable of C-N bond homolysis and subsequent recombination and/or disproportionation. It is unclear what causes these radicals to undergo recombination or disproportionation. Density Functional Theory (DFT) calculations do not provide a transition state for the recombination and disproportionation processes and therefore they cannot be used to predict the favorable reaction. Breslow intermediates formed by deprotonation of thiazolium salts and reaction with aromatic aldehydes are examples of electron rich enamines. These breslow intermediates can undergo C-N bond homolysis to form a radical pair the either recombine or disproportionate. Upon investigation of the factors influencing recombination and disproportionation, …

An Experimental Study Of Evaporites On Titan: Implications For Lake Composition And Future Missions, Ellen Czaplinski

Graduate Theses and Dissertations

Titan is the only other planetary body in the solar system with liquid on the surface. With a surface temperature and pressure of 89 – 94 K and 1.5 bar (N2), respectively, Titan’s lakes are comprised of liquid hydrocarbons, predominantly methane and ethane. Over time, Titan’s lakes may evaporate, leaving behind residual deposits (evaporites). The evaporation processes and composition of the evaporites is poorly understood. I address these outstanding questions by experimentally investigating the physical and spectral properties of evaporites at Titan surface conditions using an experimental chamber.

Chapter 1 addresses the formation of ethylene evaporites. Ethylene evaporites form more …

Assessing Biofiltration Without Ozonation For Removal Of Trihalomethane Precursors In Drinking Water At The Beaver Water District Drinking Water Treatment Plant, Sana Ajaz

Graduate Theses and Dissertations

Biofiltration without pre-ozonation has the capability to remove natural organic matter (NOM) fractions that serve as precursors of disinfection byproducts (DBPs), which include the four regulated trihalomethanes (THMs) and dichloroacetonitrile (DCAN). Rapid small-scale column tests (RSSCTs) and Pilot Plant filters operated at empty-bed contact times (EBCTs) of 4, 8, and 16 minutes were used to evaluate the performance of nutrient-amended (free ammonia and phosphorus) biofiltration for THM and DCAN precursor removal, as measured using formation potential (FP) tests. NOM surrogates – which include dissolved organic carbon (DOC), specific ultraviolet absorbance (SUVA254) and fluorescence-PARAFAC components – were measured weekly throughout the …

Influence Of Histidine Residues, Ph And Charge Interactions On Membrane-Spanning Peptides, Ashley N. Henderson

Graduate Theses and Dissertations

Designed transmembrane peptides were employed for investigations of histidine residues within the hydrophobic environment of the lipid bilayer by means of oriented solid-state deuterium NMR spectroscopy. Using the model peptide GWALP23 sequence (GGALW(LA)6LWLAGA) as a host framework, the effects of single and double histidine mutations were explored. Replacement of leucine residue 12 to polar neutral histidine had little influence on the peptide average orientation, however under strongly acidic pH conditions in DOPC bilayers, the histidine becomes positively charged (pKa 2.5) and the GWALP23-H12 peptide exits the membrane and adopts a surface-bound orientation. Conversely, mutation of leucine 14 to neutral histidine …

Interactions In The Cpsrp Dependent Targeting Of Light Harvesting Chlorophyll Binding Protein To The Thylakoid Membrane, Rory Henderson

Graduate Theses and Dissertations

Targeting of proteins is a critical component of cellular function. A universally conserved targeting system of the cytosol utilizes a signal recognition particle (SRP) to target many proteins contranslationally to the endoplasmic reticulum in eukaryotes or the inner membrane in prokaryotes. A homologous SRP system exists in the chloroplast that delivers light harvesting chlorophyll binding proteins (LHCP) to they thylakoid membrane. The chloroplast SRP (cpSRP) is a heterodimer composed of a novel 43 kDa subunit and a 54 kDa subunit homologous to a component of the SRP system, SRP54. Many details regarding the interactions between the proteins of the cpSRP …

The Role Of Organic Matter In The Fate And Transport Of Antibiotic Resistance, Metals, And Nutrients In The Karst Of Northwest Arkansas, Victor Lee Roland Ii

Graduate Theses and Dissertations

Organic matter (OM) in the environment acts as a nutrient, but may also act as a transport vector for harmful chemical compounds and bacteria. Acetate is a labile form of OM produced during fermentation in anaerobic lagoons used to store animal fecal-waste from concentrated animal feeding operations (CAFOs). Dry and liquid fertilizers from CAFOs pose a threat to groundwater by introducing excessive amounts of nutrients (e.g. OM, nitrate and ammonia), metals, and antibiotic compounds. In the epikarst of Northern Arkansas in the Buffalo River watershed additional input of labile dissolved organic carbon (DOC) from liquid CAFO waste-fertilizers was hypothesized to …

Synthesis Of Palladium And Palladium-Copper Nanostructures As Electrocatalysts, Haibin Wu

Graduate Theses and Dissertations

Pd and its alloys are alternatives of Pt as promising catalysts and electrocatalysts for many reactions. Size controlled synthesis of nanoparticles remains a major research subject, since smaller size particles show better catalytic performance. In this work, we developed a modified chemical wet method to prepare Pd and Pd-Cu nanostructures with uniform small size. Different sizes and shapes of Pd nanostructures were successfully synthesized by using the two reducing agents (i.e., L-ascorbyl-6-palmitate or phenylphosphinic acid). The reducing agents play a role to control the final morphologies and sizes of particles. The use of L-ascorbyl-6-palmitate favors to form irregular branch shapes …

Studies Toward The Total Synthesis Of Antascomicin B, David Ross Clay

Graduate Theses and Dissertations

The following dissertation describes synthetic efforts toward the synthesis of the C21-C34 fragment of antascomicin B. Our initial enzymatic approach is detailed as well as an asymmetric transfer hydrogenation (ATH) strategy that will be used in the eventual total synthesis of the molecule. Several investigations into anomalies observed during (ATH) reactions are also discussed.