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Determination Of The Effects Of Zno And Ceo2 Nanoparticles In Mesquite (Prosopis Juliflora) And Soybean (Glycine Max): Synchrotron And Spectroscopic Approaches, Jose Angel Hernandez Viezcas

Open Access Theses & Dissertations

The rapid growth of nanotechnology is exposing the environment to abnormal concentrations of engineered nanoparticles (NPs). There is concern about the unknown consequences of NPs on the environment and human health. This Dissertation has relied significantly on Synchrotron and other spectroscopic techniques to give insights on the effects, speciation and distribution of two metal oxide nanoparticles (ZnO, CeO2) on two plant species (Mesquite and Soybean). We evaluated the effects of ZnO (10 nm) and CeO2 (8 nm) NPs on a plant species native to the semi-arid regions of North America, Mesquite (Prosopis juliflora velutina). Mesquite plants grown in hydroponic culture …

Method Development For A Chemical And Biological Analysis Of Glucocorticoids In Wastewater, Maria Carmen Lozano

Open Access Theses & Dissertations

Glucocorticoids are a class of steroid hormones that can either be produced synthetically or naturally by the adrenal glands. The synthetic glucocorticoids are highly prescribed in the United States for their anti-inflammatory and immunosuppressive properties to treat a variety of ailments and diseases; however, these have been implicated in a number of adverse human conditions such as obesity, metabolic syndrome, immune-suppression, delayed puberty, adrenal insufficiency and Cushing Syndrome, among others. Ongoing research has shown that synthetic and natural hormones are transported to aquatic environments via mammalian excretion or wastewater effluent, and as a result, the release of glucocorticoids into the …

Impact Of Cerium Oxide Nanoparticles On Cilantro (Coriandrum Sativum), Maria Isabel Morales

Open Access Theses & Dissertations

Studies have shown that plants exposed to ENPs suffer different types of stress. Other studies have revealed that plants can take up and accumulate CeO2 NPs without modification. Thus, these NPs could enter the food chain through edible plants, posing a threat for human health. Cilantro (Coriandrum sativum) is a worldwide culinary and medicinal plant consumed either as a fresh herb or a spice. In this research, cilantro plants were germinated and cultivated for 30 days in organic soil treated with CeO2 NPs at concentrations varying from 0 to 500 mg kg!1. Subsequently, plant organs were analyzed by using spectroscopic …

Photochemical Synthesis Of Amino Acid And Peptide Oxo-Esters, Alfredo Ornelas

Open Access Theses & Dissertations

Amino acid and peptide oxo-esters have played an important role in peptide chemistry for many years. Various amino acid esters are commonly used as protecting groups for peptide synthesis in solution. Moreover, activated phenyl ester derivatives have been used for chemical ligation of peptides. However, the synthesis of amino acid and peptide oxo-esters is commonly performed under acidic or basic conditions. Under acidic conditions, acid-sensitive protecting groups may be cleaved, and under basic conditions racemization of amino acid esters is a common problem. Here we present the photochemical synthesis of amino acid and peptide oxo-esters. Based on the photochemical properties …

Novel Copper (Ii) Mediated Transfection Nano-Systems And Biological Properties Of Pyridinium Surfactants, Sarit Pal

Open Access Theses & Dissertations

Efficacy of gene therapy is relied upon the improvement of gene delivery vectors into mammalian cells. Although viral-based polynucleotide carriers are still considered as the most common method for gene delivery but the cost effectiveness, nonspecific lethal immune response has evoked the renaissance of non-viral synthetic delivery systems. An initial discovery by Felgnar et al showed Cationic Liposomes (CLs) (having an overall positive charge) when mixed with DNA to form CL-DNA complexes can enhance the transfer of polynucleotides into cells followed by its expression. Presently, a flurry of experimental works is taking place for the better understanding of structural characterization …

Effects Of Temperature On The Physicochemical Properties Of Traditionally Processed Vegetable Oils And Their Blends, Fn Ngassapa, Ss Nyandoroa, Tr Mwaisaka

Tanzania Journal of Science

The quality and stability of traditionally processed palm, sunflower and sesame oils and their blends as affected by temperature were evaluated by analyzing their physicochemical properties which included acid, saponification, peroxide, iodine values and refractive indices.. The initial quality of traditionally processed oils studied was found to be within the specifications of TZS and Codex requirements. The results further indicate that the quality of both unblended and blended traditionally processed vegetable oils deteriorate significantly at elevated temperatures (p < 0.05). However, the blends showed relatively better quality and stability than the unblended ones whereby the formulations of palm oil (PO) and sesame oil (SSO) appeared to be more stable than those of PO and sunflower oil (SO). This work suggests that blending of traditionally processed PO, SO and SSO improves the quality and stability of these oils.

Molecularly Imprinted Polymer Technology: A Powerful, Generic, Facile And Cost Effective Alternative For Enantio-Recognition And Separation: A Glance At Advances And Applications, Jyn Philip, Dms Mosha

Tanzania Journal of Science

The emerging Molecularly Imprinted Polymer (MIP) technology has yielded proof of concept, harnessing nature’s fundamentals to yield recognition receptor mimics from the miniaturized basics, borrowing on the ground rules, but conveniently avoiding the complexity, fragility, instability, costs and ethics of animal based bio-affinity matrices. Thus, the impact of bio-sciences on the future of technology is not via direct use of the molecules, but rather the lessons learned. Molecular imprinting is a powerful specialty representing the generic, cost effective and facile alternative for preparation of synthetic custom-tailored receptors. It achieves this via creation of specific selective recognition sites for a pre-determined …

Theoretical Study Of Physiochemical Properties Of Insulin-Like Growth Factor 1, A Ilkhani

Tanzania Journal of Science

The computational approach to studying structural changes in a wide range of physical and biological problems, the empirical force fields, have great difficulty in simulating folding of Insulin-like Growth Factor 1 (IGF-1). In an effort to understand the conformational preferences that may be attributed to stereoelectronic effects, a number of computational studies were carried out. Monte Carlo, Molecular Dynamics and Langevin simulation methods by MM+, AMBER and OPLS force fields of calculations have been performed on IGF-1 as growth factors. The parameters of a minimized structure of IGF-1, calculated potential energy for important dihedral angles and the effect of temperature …

Computational Chemistry Capacity Building In An Underprivileged Context: Challenges, Outcomes And Perspectives, L Mammino

Tanzania Journal of Science

Computational chemistry is a fast developing branch of modern chemistry, focusing on the study of molecules to enable better understanding of the properties of substances. Its applications comprise a variety of fields, from drug design to the design of compounds with desired properties (e.g., catalysts with specific actions) and to ample overlaps with nanotechnology. However, despite its relevance, the presence of computational chemistry research in Sub-Saharan Africa is still scarce, practically absent in many institutions. Bridging the gap with the other continents requires the identification of capacity building options that may enable a rapid growth. The recent experience at the …

Kinetic Study Of Photoelectrochemical Oxidation Of Lignin Model Compounds On Tio2 Nanotubes, Min Tian, Daniel Liba, Aicheng Chen

Journal of Electrochemistry

In this study, TiO₂ nanotubes were prepared via the electrochemical oxidation of titanium substrates in a non-aqueous electrolyte and their morphology and microstructures were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photoelectrochemical oxidation of two lignin model compounds, 1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanediol (DMP) and 3-hydroxy-1-(3,4-dimethoxyphenoxy)-2-(2-methoxyphenoxy)-1,3-propanone (HDM), was investigated. A new band appeared at ~304 nm during the photoelectrochemical oxidation of DMP. The rate of DMP intermediate formation was amplified with the increase of initial concentrations, while it was diminished with increased temperature. Despite the similarity in structure between HDM and DMP, there are only small increases in absorbance …

Polymorphism And Polyamorphism In Bilayer Water Confined To Slit Nanopore Under High Pressure, Jaeil Bai, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A distinctive physical property of bulk water is its rich solid-state phase behavior, which includes 15 crystalline (ice I–ice XIV) and at least 3 glassy forms ofwater, namely, low-density amorphous, highdensity amorphous, and very-high-density amorphous (VHDA). Nanoscale confinement adds a new physical variable that can result in a wealth of new quasi-2D phases of ice and amorphous ice. Previous computer simulations have revealed that when water is confined between two flat hydrophobic plates about 7–9 Å apart, numerous bilayer (BL) ices (or polymorphs) can arise [e.g., BL-hexagonal ice (BL-ice I)]. Indeed, growth of the BL-ice I through vapor deposition on …

A Comparison Of Boltzmann And Gibbs Definitions Of Microcanonical Entropy For Small Systems, Randall B. Shirts

Faculty Publications

Two different definitions of entropy, S= klnW, in the microcanonical ensemble have been competing for over 100 years. The Boltzmann/Planck definition is that W is the number of states accessible to the system at its energy E (also called the surface entropy). The Gibbs/Hertz definition is that W is the number of states of the system up to the energy E (also called the volume entropy). These two definitions agree for large systems but differ by terms of order N^-1 for small systems, where N is the number of particles in the system. For three analytical …

Ultra-Stable Protein-Polymer Bioconjugates, Kyle S. Cole

Master's Theses

No abstract provided.

The Lyme Disease Spirochete In Tick Species Collected From Warren County, Kentucky, Cheryl C. Onwu

Mahurin Honors College Capstone Experience/Thesis Projects

The overall goal of this present study was to determine the prevalence of the Lyme disease spirochete, Borrelia burgdorferi, in south central Kentucky. A survey of ticks collected from a single location in Warren County, Kentucky was conducted between the months of April and June, 2010. A total of 293 ticks were collected. Three species were identified: 264 (91.7 %) of the ticks were Amblyoma americanum, 18 (6.6%) were Dermacentor variabilis, and 1 (0.35%) was Ixodes scapularis. The ten remaining ticks were immature nymphs and could not be identified. After identifying the species and sex of …

Reaction Of Halogenated Hydrocarbons With Cysteine And Nucleotides, Brittany S. Morgan

Mahurin Honors College Capstone Experience/Thesis Projects

Our objective is to develop a simple, inexpensive model to better understand the biologically relevant reactions of halogenated hydrocarbons and characterize them by NMR spectroscopy. We currently have a model that mimics the adduct created by the reaction of ethylene dibromide (a known toxin and carcinogen) with cysteine and guanosine 5’-monophosphate. Early attempts led to side products including ethylene oxide and ethylene glycol; however, our most promising method to date reacts cysteine with 2-bromoethanol in sodium methoxide/methanol followed by reaction of the 2-hydroxyethyl adduct with HCl and later with guanosine 5’-monophosphate. By reacting other halogenated hydrocarbons through the same method, …

Synthesis And Characterization Of Metallocorrole And Metalloporphyrin Complexes For Catalytic Oxidations, Zhibo Yuan

Mahurin Honors College Capstone Experience/Thesis Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in nature, namely the cytochrome P450 enzymes. Metal porphyrin complexes have been the center of research as catalysts in this context. This study focuses on the synthesis of porphyrin and corrole macrocyclic ligands and the corresponding ruthenium and iron complexes which are fully characterized by UV-vis and NMR spectroscopies.

The catalytic oxidation reactions towards organic sulfides by these metal complexes were also studied. Two ruthenium porphyrin complexes …

Water-Soluble Deep-Cavity Cavitands: Synthesis, Molecular Recognition, And Interactions With Phospholipid Membranes, Sarah E. Ioup

LSU New Orleans Theses and Dissertations

Water-soluble deep-cavity cavitands provide a rare opportunity to study self-assembly driven by the hydrophobic effect. These molecular hosts dimerize in the presence of certain guest molecules to form water-soluble molecular capsules. These systems have given rise to numerous novel chemical phenomena and have potential use in drug delivery. The host octaacid (OA) has been particularly well-characterized, but studies are limited to basic pH because of limited host solubility.

Herein we report an improved synthesis of OA and the syntheses of three new water-soluble deep-cavity cavitands. The new hosts are soluble at neutral pH, increasing relevance for biological studies. The new …

Dissolved Organic Matter Composition And Bioavailability Reflect Ecosystem Productivity In The Western Arctic Ocean, Yuan Shen, Cedric Fichot, Ronald Benner

Faculty Publications

Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High concentrations and yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting …

Microfluidic Devices With Integrated Sample Preparation For Improved Analysis Of Protein Biomarkers, Pamela Nsang Nge

Theses and Dissertations

Biomarkers present a non-invasive means of detecting cancer because they can be obtained from body fluids. They can also be used for prognosis and assessing response to treatment. To limit interferences it is essential to pretreat biological samples before analysis. Sample preparation methods include extraction of analyte from an unsuitable matrix, purification, concentration or dilution and labeling. The many advantages offered by microfluidics include portability, speed, automation and integration. Because of the difficulties encountered in integrating this step in microfluidic devices most sample preparation methods are often carried out off-chip. In the fabrication of micro-total analysis systems it is important …

Acid-Base Catalysis In Proton-Coupled Electron Transfer Reactions (Pcet): The Effects Of Brönsted Bases On The Oxidation Of Glutathione And Hydroquinone, Ramos Jonnathan Medina

Theses and Dissertations

This thesis presents the results and discussion of the investigation of the effects of Brönsted bases on the kinetics and thermodynamics of two proton-coupled electron transfer processes: the mediated oxidation of glutathione and the electrochemical oxidation of hydroquinone. Proton-coupled electron transfer (PCET) is the name given to reactions that involve the transfer of electron(s) accompanied by the exchange of proton(s). PCETs are found in many chemical and biological processes, some of current technological relevance such as the oxygen reduction reaction in fuel cells, which involves the transfer of four electrons and four protons (4e-, 4H+); or the splitting of water …

Hydrothermal Chemistry Of The M(I,Ii)/Paha/Anion System, Kari Ann Darling

Chemistry - Dissertations

This research encompasses the detailed investigation of the design and synthesis of metal organic framework (MOF) materials involving the M(I,II)/ polyazaheterocycle/anion system in order to expand our understanding of the principles which render the chemistry more controllable and predictable. In addition, this research investigates the development of properties in these classes of compounds. Furthermore, it has been demonstrated that hydrothermal reaction conditions of stoichiometry, pH, and temperature can influence the identity of the products.

The structural versatility of the M(I,II)/polyazaheterocycle/anion system for M = Cu(I,II), Co(II), Ni (II), Zn (II), and Cd(II) and where the anion is F^-, …

Mechanism Of Action And Gold Nanoparticle Delivery Of Pt(Iv) Prodrugs Of Cisplatin, Yi Shi

Chemistry - Dissertations

The antitumor effects of platinum(IV) complexes, considered prodrugs for cisplatin, are believed to be due to biological reduction of Pt(IV) to Pt(II), with the reduction products binding to DNA and other cellular targets. In this work we used pBR322 DNA to capture the products of reduction of oxoplatin, c,t,c-[PtCl₂(OH)₂(NH₃)₂], 2, and a carboxylate-modified analog, c,t,c-[PtCl₂(OH)(O₂CCH₂CH₂CO₂H)(NH₃)₂], 3, by ascorbic acid (AsA) or glutathione (GSH). Since carbonate plays a significant role in the speciation of platinum …

Phosphorus Transport And Distribution In Kentucky Soils Prepared Using Various Biochar Types, Anvesh Reddy

Masters Theses & Specialist Projects

Conserving the environment is an issue that is gaining popularity day by day. Phosphorus transfer from agricultural soils is an important environmental issue that is being closely observed as the transport of phosphorous to water bodies is adversely affecting water quality due to accelerated eutrophication. It is important to establish phosphorous models that accurately account for soil test phosphorous. Standard models like SWAT (Soil and Water Assessment Tool) and EPIC (Environmental Policy Integrated Climate) were designed for serving this purpose. They are now used as the basis for developing new models that can more accurately account for the phosphorus transport, …

On Metal Synthesis Of Some Substituted Rhenium And Manganese Complexes, Jaron Michael Thomas

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (i.e. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to their non-aromatic analogs (i.e. polyacetylene). Our current interest focus upon the potential role of metal ligand bound pyridazines as the next generation of electronic devices that utilize the metal ligands bound to organics as the semiconducting material. Pyridazine is a 6-membered aromatic ring with two adjacent nitrogen atoms. These are promising candidates for a variety of materials and commercial applications; but they are difficult to get a metal ligand to fuse …

Designing Tools For Studying The Dynamic Glycome, John F. Rakus

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Judging A Book By Its Cover: Using Lectin Microarrays To Identify How Glycosylation Is Regulated, John F. Rakus

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Supramolecular Sensor For Cancer-Associated Nitrosamines, Tsuyoshi Minami, Nina A. Esipenko, Ben Zhang, Maria E. Kozelkova, Lyle Isaacs, Ryuhei Nishiyabu, Yuji Kubo, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

A supramolecular assay based on two fluorescent cucurbit[n]uril probes enables the recognition and quantification of nitrosamines, including cancer-associated nitrosamines, compounds that are difficult to recognize. The cross-reactive sensor leverages weak interactions and competition among the probe, metal, and guest, yielding high information density in the signal output (variance) and enabling the recognition of structurally similar guests.

G-Ruption: The Third International Meeting On G-Quadruplex And G-Assembly, Liliya A. Yatsunyk, T. M. Bryan, F. B. Johnson

Chemistry & Biochemistry Faculty Works

A three and a half day conference focusing on nucleic acid structures called G-quadruplexes (G4s) and other guanine-based assemblies was held in Sorrento. Italy (June 28-July 1, 2011) and featured 35 invited talks and over 89 posters. The G-quadruplex field continues to expand at an explosive rate with the emergence of new connections to biology, chemistry, physics, and nanotechnology. Following the trend established by the previous two international G4 meetings, the conference touched upon all these areas and facilitated productive exchanges of ideas between researchers from all over the world.

Direct Analysis Of Hops By Leaf Spray And Paper Spray Mass Spectrometry, Kari Blain

Masters Theses

The objective of this research is to develop a new and innovative method of hops analysis, which is much faster than standard testing methods, as well as reduce the amount of consumables and solvent used. A detailed discussion on the development of an ambient ionization mass spectrometry method called paper spray (PS-MS) and leaf spray (LS-MS) mass spectrometry will be presented. This research investigates the use of PS-MS and LS-MS techniques to determine the α- and β- acids present in hops. PS-MS and LS-MS provide a fast way to analyze hops samples by delivering data as rapidly as a UV-Vis …

Nucleophilic Carbon-Carbon Bond-Forming Reactions Of 2-Methylenetetrahydropyrans, Laura Jean Bateman

Chemistry - Dissertations

Reactions with 2-methylenetetrahydropyrans are underutilized in the literature, especially with respect to general methods demonstrating their nucleophilic nature. This work provides three general methods toward the synthesis of 2-β-oxygenated pyranyl substrates, which are key structural components of many biologically active polyketides and natural products.

The use of exocyclic enol ethers as nucleophiles was first demonstrated as a general process in three-component coupling reactions with secondary nucleophiles. The 2-β-hydroxy tetrahydropyran products were obtained in good to excellent yields through promotion with stoichiometric levels of titanium(IV) chloride at reduced temperatures. Only activated aldehydes or ketones worked as efficient coupling partners for this …