Chemistry Commons^™

Soil And Biosolid Nano- And Macro-Colloid Properties And Contaminant Transport Behavior, Jessique L. Ghezzi

Theses and Dissertations--Plant and Soil Sciences

Despite indications that they are potential contaminant transport systems and threats to groundwater quality, very little effort has been invested in comparing contaminant transport behavior of natural environmental nanocolloids and their corresponding macrocolloid fractions in the presence of As, Se, Pb, and Cu contaminants. This study involved physico-chemical, mineralogical, stability and contaminant-transport characterizations of nano- (< 100 nm) and macro-colloids (100-2000 nm) fractionated from three Kentucky soils and one biosolid waste. Particle size was investigated with SEM/TEM and dynamic light scattering. Surface reactivity was estimated using CEC and zeta potential. Mineralogical composition was determined by XRD, FTIR, and thermogravimetric analyses. Sorption isotherms assessed affinities for Cu²⁺, Pb²⁺, AsO₃^-, and SeO₄^-2 contaminants, while settling kinetics experiments of suspensions at 0, 2 and 10 mg/L contaminants determined stability and transportability potential. Undisturbed 18x30 cm KY Ashton Loam soil monoliths were also used for …

Monitoring The Influence Of Acid Deposition On Soil And Implications To Forest Health In The Daniel Boone National Forest, Tyler M. Sanderson

Theses and Dissertations--Forestry and Natural Resources

Combustion of fossil fuels has contributed to many environmental problems including acid deposition. The Clean Air Act (CAA) was created to reduce ecological problems by cutting emissions of sulfur and nitrogen. Reduced emissions and rainfall concentrations of acidic ions have been observed since the enactment of the CAA, but soils continue to receive some acid inputs. Soils sensitive to acid deposition have been found to have low pH, a loss of base cations and a shift in the mineral phase controlling the activity of Al³⁺ and/or SO₄^2-. If inputs continue, soil may be depleted of base …

Quantification Of Factors Governing Drug Release Kinetics From Nanoparticles: A Combined Experimental And Mechanistic Modeling Approach, Kyle Daniel Fugit

Theses and Dissertations--Pharmacy

Advancements in nanoparticle drug delivery of anticancer agents require mathematical models capable of predicting in vivo formulation performance from in vitro characterization studies. Such models must identify and incorporate the physicochemical properties of the therapeutic agent and nanoparticle driving in vivo drug release. This work identifies these factors for two nanoparticle formulations of anticancer agents using an approach which develops mechanistic mathematical models in conjunction with experimental studies.

A non-sink ultrafiltration method was developed to monitor liposomal release kinetics of the anticancer agent topotecan. Mathematical modeling allowed simultaneous determination of drug permeability and interfacial binding to the bilayer from release …

Applications Of Gas Chromatography/Mass Spectrometry And Capillary Electrophoresis For The Analysis Of Lignocellulosic Biomass Pretreatment, Dawn M. Kato

Theses and Dissertations--Chemistry

The focus of this dissertation centers on the development and applications of gas chromatography/mass spectrometry and capillary electrophoresis methodologies to quantify monomeric compositions of the β-O-4 linkages in lignin. Pretreatment is a required step in the utilization of lignocellulosic biomass for biofuels. Lignin is the target of pretreatment because it hinders the accessibility of enzymes and chemicals to cellulose. The effects of pretreatment are commonly assessed utilizing enzymatic saccharification and lignin assays. However, these techniques do not elucidate the effects of pretreatment on the monomeric make up of lignin.

The overarching hypothesis of this dissertation is that changes in individual …

Nuclear Structure In Transitional Regions: Studies Of ¹³²,¹³⁴Xe And Lifetimes In The Stable Zr Nuclei With The (N,N′Γ) Reaction, Erin Elizabeth Peters

Theses and Dissertations--Chemistry

Nuclei at closed shells tend to be spherical and are well-described by the shell model, while those between closed shells are deformed and better described by collective models. The nuclei which are in transitional regions between spherical and deformed may be studied to gain insight into the nature of this transition. The stable isotopes of zirconium and xenon span such transitional regions and are the subject of this dissertation. Gamma-ray spectroscopy following inelastic neutron scattering has been performed on the stable isotopes of Zr as well as ^132,134Xe at the University of Kentucky Accelerator Laboratory. Level lifetimes have been …

Methods Development In Biological Mass Spectrometry: Application In Glycoproteomics, Sanja Trajkovic

Theses and Dissertations--Chemistry

Proteomics refers to global characterization of the full set of proteins present in a biological sample. Various analytical disciplines contribute to proteomics but mass spectrometry became method of choice for analysis of complex protein samples.

Mass spectrometry allows for high throughput analysis of the proteome but, moreover, it has the ability to acquire higher-order information such as post-translational modifications (PTM). Glycosylation is the most abundant PTM on eukaryotic proteins.

This dissertation will focus on method development for structural proteomics that will be utilized to explain the glycoproteome of obligate intracellular protozoan parasite Toxoplasma gondii as a model system.

Optimization of …

Temperature-Dependent Tunable Photoluminescence Properties Of Carbon Nanodots Derived From Polyethylene Glycol, Sin Hea Yeom

Theses and Dissertations--Chemistry

Fluorescent carbon dots (C-dots) are well known for their low cell-cytotoxicity, biocompatibility, low preparation cost, excitation dependent photoluminescence, and excellent photostability. Typically, raw C-dots have low quantum efficiency and thus researchers have been utilizing biocompatible polymers such as polyethylene glycol (PEG) as a passivation agent in order to increase fluorescence signal. In this work, we report fluorescent self-passivated carbon nanodots (CNDs) synthesized from PEG by using it as a carbon source as well as a passivating agent. Importantly, the addition of graphene quantum dots (GQDs) during the synthesis of self-passivated CNDs can tune photoluminescence property. The results of bioimaging and …

Salen Aluminum Compounds In The Dealkylation And Detection Of Organophosphates, Rahul R. Butala

Theses and Dissertations--Chemistry

The focus of this dissertation is the use of aluminum Schiff base compounds, Salen(^tBu)AlBr (SAB), in the dealkylation and detection of organophosphates (OPs). Three SAB compounds, Salen(^tBu)AlBr (1), Salpen(^tBu)AlBr (2), and Salophen(^tBu)AlBr (3) were used to dealkylate a variety of trialkyl OPs. These reactions lead to unique organic-soluble aluminum phosphate compounds containing six-coordinate aluminum. Examples include [salen(^tBu)AlOP(O)(OCH₃)₂]_n (4), [salen(^tBu)AlOP(O)(OCH₂CH₃)₂]_n (5), [salen(^tBu)AlOP(O)(OPh)₂]_{n …}

Electron And Ion Spectroscopy Of Metal Hydrocarbon Complexes, Sudesh Kumari

Theses and Dissertations--Chemistry

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations.

In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes …

Structures And Electronic States Of Small Group 3 Metal Clusters, Lu Wu

Theses and Dissertations--Chemistry

Group 3 metal clusters are synthesized by laser vaporization in a pulsed cluster beam source and identified with laser ionization time-of-flight mass spectrometry. The adiabatic ionization energies and vibrational frequencies of these clusters are measured using mass-analyzed threshold ionization (MATI) spectroscopy. Their structures and electronic states are determined by combining the MATI spectra with quantum chemical calculations and spectral simulations. This dissertation focuses on the study of several small molecules, which include LaO₂, La₂, M₂O₂, M₃O₄, M₃C₂, and La₃C₂O, where …

Laser Spectroscopy Of Radicals Containing Group Iiia And Va Elements, Robert A. Grimminger

Theses and Dissertations--Chemistry

Radicals are interesting to study because of importance in so many processes such as semiconductor growth or stellar evolution. Laser induced fluorescence (LIF) and wavelength resolved emission spectra of jet cooled HPS, HAsO, AsD₂, H₂PS, and F₂BO have been measured using the pulsed discharge jet technique.

Several bands in the à ¹A′′ − X̃ ¹A′ transition of HPS were observed and assigned with the help of ab initio calculations. The ab initio geometries showed that HPS does not follow Walsh’s predictions for the angle change upon electronic excitation; Walsh predicts an increase …

Addressing Public Health Risks Of Persistent Pollutants Through Nutritional Modulation And Biomimetic Nanocomposite Remediation Platforms, Bradley J. Newsome

Theses and Dissertations--Chemistry

Due to their relative chemical stability and ubiquity in the environment, chlorinated organic contaminants such as polychlorinated biphenyls (PCBs) pose significant health risks and enduring remediation challenges. Engineered nanoparticles (NPs) provide a novel platform for sensing/remediation of these toxicants, in addition to the growing use of NPs in many industrial and biomedical applications, but there remains concern for their potential long-term health effects. Research highlighted herein also represents a transdisciplinary approach to address human health challenges associated with exposure to PCBs and NPs. The objectives of this dissertation research are two-fold, 1) to develop effective methods for capture/sensing and remediation …

Electrode And Electrolyte Additives For Lifetime Extension In Lithium-Ion Batteries, Kishore Anand Narayana

Theses and Dissertations--Chemistry

Lithium-ion batteries (LIBs) are the most commonly used type of rechargeable batteries with a global market estimated at $11 billion, which is predicted to grow to $60 billion by 2020. The global commercialization of Li-ion batteries is impeded by issues such as poor cycle life (5000 cycles achieved in some LIBs) in high energy and power density applications because of the rising internal resistance due to aging and safety concerns such as overcharge which ultimately leads to thermal runaway and explosions. A battery’s performance mainly depends on external factors such as electrode thickness and degree of compacting, and the type …

Cross Photoreaction Of Pyruvic And Glyoxylic Acids In Model Aqueous Aerosols, Shasha Xia

Theses and Dissertations--Chemistry

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. Aerosols from natural and anthropogenic sources can be primary organic aerosols (POA), which are directly emitted to the atmosphere, or secondary organic aerosols (SOA) that are formed from chemical reactions of gas-phase precursors. At variance with the well investigated formation of SOA from gas phase precursors, the chemistry of aqueous SOAs that contribute to the total SOA budget remains unknown. Field measurements have revealed that carboxylic, dicarboxylic and oxocarboxylic acids are abundant species present in SOAs. This thesis …

A Study Of Lignin Depolymerization By Selective Cleavage Of The Cα-Cβ Linkages In Lignin Model Compounds Via Baeyer-Villiger Oxidation & An Investigation Of The Channeling Reaction In Nitrogen-Doped Multiwalled Carbon Nanotubes (N-Mwcnts), Nikhil Dilip Patil

Theses and Dissertations--Chemistry

A STUDY OF LIGNIN DEPOLYMERIZATION BY SELECTIVE CLEAVAGE OF THE Cα-Cβ LINKAGES IN LIGNIN MODEL COMPOUNDS VIA BAEYER-VILLIGER OXIDATION

Lignin is amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective …