Physical Sciences and Mathematics Commons^™

Methods Development And Application Of Two Dimensional Chromatography And Tandem Mass Spectrometry In Proteomics, Brett Romain Wenner

University of Kentucky Doctoral Dissertations

Although molybdenum blue solutions have been known for more than twocenturies, an understanding of their chemical nature is only beginning to emerge.This dissertation aimed at elucidating the structural nature of the polydisperse,nanoscopic components in the solution phases and the solid states of partiallyreduced polyoxomolybdate (Mo-POM). The study offered at least fourcontributions to the area: (1) a rational protocol for the molecular recognition ofMo-POM with de novo organic hosts. (2) demonstration of kinetic precipitation ofa dynamic mixture of polyoxomolybdates and application of the technique to thestudy of the dynamic mixture by TEM (3) characterization of the Mo-POMnanostructures by an unusual combination …

Mapping Of Diepoxybutane Damage In The Cytochrome B Domain Of Mitochondrial Dna And The Β-Globin Domain Of Nuclear Chicken Dna Using Quantitative Pcr, Justin Juskewitch

Honors Theses

Diepoxybutane (DEB), a known industrial carcinogen, reacts with DNA primarily at the N7 position of deoxyguanosine residues and creates interstrand cross-links at the sequence 5'-GNC. Since N7-N7 cross-links cause DNA to fragment upon heating, quantative polymerase chain reaction (QPCR) is being used in this experiment to measure the amount of DEB damage (lesion frequency) with three different targets-mitochondrial (unpackaged), open chromatin region, and closed chromatin region. Initial measurements of DEB damage within these three targets were not consistent because the template DNA was not the limiting reagent in the PCR. Follow-up PCR trials using a limiting amount of DNA are …

Altered Phosphorylation Of [Beta]-Catenin In Glucocorticoid Treated 235-1 Rat Pituitary Tumor Cells, Susie K. Saunders

Theses, Dissertations and Capstones

Beta-catenin is an essential cell adhesion and signaling protein, associated with high prolactin levels in rat pituitary tumor cells. It has been shown that phosphorylation affects the location and activity of b-catenin. Glycogen synthase kinase (GSK3-b) is a serine-threonine kinase that phosphorylates b-catenin on N-terminal residues, targeting it for proteasomal degradation. Studies have shown that C-terminal tyrosine phosphorylation decreases the association of b-catenin with cadherin. In 235-1 rat pituitary tumor cells, our lab has shown that the glucocorticoid analog dexamethasone (Dex) decreases the half- life of b-catenin while increasing the activity of GSK3-b. The current study was undertaken to examine …

Semi-Biosynthesis Of Dna Nanostructures, Aoune Barhoumi

Theses, Dissertations and Capstones

Nanotechnology refers to all technologies aiming to build objects, make measurements, and carry out processes on the nanometer length scale. In particular molecular nanotechnology exemplifies the so-called "bottom up" approach, which is briefly defined as the ability to build useful nanostructures with molecular precision, such as molecular machinery. Such capability for controlling matter at the molecular scale has always been the dream of scientists.

All living things are nanofoundries. Billions of years ago, nature perfectly provided all living things with the most accurate biological nanotechnology systems. Cellular internal dynamics, communicative resonance in protein conformational states, viruses as microreplicators, nanoscale life …

Ac Frequency Dependence Of Electroluminescent Zns Phosphor Panel Color, Farrah Shantell Boggess-Machado

Theses, Dissertations and Capstones

In this study, electroluminescent panels manufactured by Meadow River Enterprises were used to study the AC frequency dependence of their color. A project was developed to acquire their emittance color at various frequencies. Three frequencies were selected for the investigation. Data, obtained by measuring the spectrum at a constant excitation frequency, were taken for each of the three standard frequencies: 200 Hz, 1500 Hz, and 20 kHz. In general the higher the frequency, the bluer the emittance color of the panel. The lower the frequency, the more green the panel became. An explanation for this phenomenon, the frequency dependence of …

Experimental Studies On Nucleation, Nanoparticle's Formation And Polymerization From The Vapor Phase, Victor Maher Abdelsayed

Theses and Dissertations

This research is divided into three major parts. In part I, the critical supersaturations required for the homogeneous nucleation of 2,2,2-trifluorothanol (TFE) vapor have been measured over a temperature range (266-296 K) using an upward thermal diffusion cloud chamber (DCC). The measured supersaturations are in agreement with the predictions of both the classical and the scaled theory of nucleation. Moreover, the condensation of supersaturated TFE vapor on laser-vaporized magnesium nanoparticles has been studied under different experimental conditions, such as the supersaturation, the pressure and the electric field. In part II, the laser vaporization controlled condensation (LVCC) technique was used to …

Electron Transfer In Phosphido-Bridged Complexes, Pradeep N. Perera

Masters Theses

No abstract provided.

Iron-Promoted Remediation Of Atrazine: Solution And Amended Sandy Column Studies, Donghua Zeng

Masters Theses

No abstract provided.

Gas Phase Studies Of Molecular Clusters Containing Metal Cations, And The Ion Mobility Of Styrene Oligomers, Edreese Housni Alsharaeh

Theses and Dissertations

This study is divided into three parts. Part I deals with the mechanism of the self-initiated polymerization (or thermal polymerization) of styrene in the gas phase. In this work, we present the first direct evidence for the thermally self-initiated polymerization of styrene in the gas phase. Our approach is based on on-line analysis of the gas phase Oligomers by mass-selected ion mobility. The mobility measurements provide structural information on the ionized oligomers based on their collision cross-sections (Ω) which depend on the geometric shapes of the ions. Theoretical calculations of possible structural candidates of the Oligomers ions are then used …

Stability And Recovery Of Rna In Biological Stains, Mindy Eileen Setzer

Electronic Theses and Dissertations

In theory, RNA expression patterns, including the presence and relative abundance of particular RNA species, provide cell and tissue specific information that could be of use to forensic scientists. An mRNA based approach could allow the facile identification of the tissue components present in a body fluid stain and conceivably could supplant the battery of serological and biochemical tests currently employed in the forensic serology laboratory. Some of the potential advantages include greater test specificity, and the ability to perform simultaneous analysis using a common assay format for the presence of all body fluids of forensic interest. In this report, …

Method For Determination Of Singlet Oxygen Quantum Yields For New Fluorene-Based Photosensitizers In Aqueous Media For The Advancement Of Photodynamic Therapy, Wade William Grabow

Electronic Theses and Dissertations

Photodynamic therapy (PDT) has been investigated over the past three decades and is currently an approved therapeutic modality for skin cancer, the treatment of superficial bladder, early lung and advanced esophageal cancers, and age-related macular degeneration in a number of countries. In PDT, the absorption of light by a chromophore generates cytotoxic species such as reactive singlet oxygen, leading to irreversible destruction of the treated tissue. The measurement of the singlet oxygen quantum yield is an important determinant used to evaluate the efficiency of new photodynamic therapy agents developed in the laboratory, to screen potential photosensitizers in aqueous media.The singlet …

Mitochondrial Dna Analysis By Pyrosequencing, Patsy-Ann Susan Hastings

Electronic Theses and Dissertations

Mitochondrial DNA (deoxyribo nucleic acid) is typically used in forensic casework when small quantities of high molecular weight quality DNA is not expected to be present thus negating the chances of obtaining usable nuclear DNA. Typical samples that utilized mitochondrial DNA analysis are: hair, bones, teeth, ancient remains (samples or remains that are at least 100 years old) or very old samples (samples that are less than 100 but greater than 10 years old). The current method used to evaluate mitochondrial DNA is Sanger sequencing. Although robust, it is also time consuming and labor intensive, on the other hand pyrosequencing …

Part I: Evaluation Of Russian Synthetic Compounds As A Potential Source Of New Drug Leads Agains Breast And Colon Cancer Part Ii: Isolation Of Beta-Amyrin Formate From Eucalyptus Viminalis Labill And Investigation Of Its Colon Cancer Activity, Mihaela Cohanoschi

Electronic Theses and Dissertations

Although modern medicine made great steps toward curing most diseases considered deadliest, yet cancer remains one of the major public health problems. The first part of this thesis investigates a new source of selective compounds that are potential candidates against cancer. Fifteen Russian compounds were tested in order to establish their efficiency against two types of cancer: human breast SK-Br-3 and colorectal carcinoma HT-29. The bioassay results show that seven of the new synthetic Russian compounds can be considered new drug leads, based upon their low toxicity and efficacy in slowing the growth of human breast cancer and colon cancer …

Synthesis And Polymerization Of Bifunctional Five-Membered Cyclic Dithiocarbonates And Their Use As Stabilizers For Magnetic Nan, Mohammed Daoudi

Electronic Theses and Dissertations

Novel bifunctional five-membered cyclic dithiocarbonates (1,3-oxathiolane-2-thione)s were synthesized by the reactions of the corresponding bifunctional oxiranes (epoxides) with carbon disulfide at room temperature with lithium bromide as catalyst. Full characterization of these monomers was performed including elemental analysis, proton and carbon nuclear magnetic resonance (NMR) spectroscopy, gas chromatography-mass spectroscopy, and Fourier transmission infrared (FTIR) spectroscopy. The polyaddition polymerization of 1,3-oxathiolane-2-thione with 1,4-diaminobutane at room temperature resulted in a poly(thiourethane) material. The latter undergoes crosslinking due probably to the autooxidation of the product and formation of disulfide linkages. The five-membered cyclic dithiocarbonate, 5-decyl-1,3-oxathiolane-2-thione, was used a model to demonstrate the usefulness …

Synthesis Of A Novel Family Of Amide Derivatives Of Podocarpic Acid, Dao Nguyen

Electronic Theses and Dissertations

As a class, amides are of great interest in biological studies and pharmaceutical application. In this work, podocarpic acid, a natural tricyclic diterpene, derived from Podocarpus species, has been employed to form a novel family of amide derivatives which will later be studied for their potential as new drug leads. Novel amide derivatives of podocarpic acid were synthesized from podocarpic acid in three steps. The first step involved methylation with dimethylsulfate to form methyl-O-methylpodocarpate. This step was followed by iodination with iodine to give iodomethyl-O-methylpodocarpate. Finally amidation with various aliphatic amides using a copper catalyst yielded four amide derivatives of …

The Design And Development Of A Comprehensive 49 Locus Y-Str Database For Major U.S. Populations, Paulina Niki Berdos

Electronic Theses and Dissertations

The establishment of a U.S. National Y-STR reference database from a variety of geographically and ethically diverse populations is essential to facilitate the generation of reliable estimates of Y-STR haplotype frequencies. Such multi-locus haplotype frequencies are required to provide a statistical estimate of the significance of a match. Y-STR loci, unlike traditional STR markers, are not independent of one another and are co-inherited as extended haplotypes of linked markers. The estimation of the frequency of occurrence of a particular haplotype therefore necessitates the use of a counting method, which means that the significance of many matches is dependent upon the …

Block Copolymer Stabilized Self-Assembled Magnetic Nanoparticles, Li Zhang

Electronic Theses and Dissertations

Magnetic materials are currently being developed in the areas of pharmacology and medicinal chemistry for use in applications such as drug delivery and magnetic resonance imaging. Magnetic fluids are being used in audio equipment and hard disk drives. Their suspension in a particular fluid is promoted by the adsorption or reaction of steric or electrostatic stabilizers, which are appropriate for the particular medium. Critical to the success of these magnetic fluids is the development of the steric stabilizers, which must prevent the coagulation of the metal particles. Polymeric materials are one of the most suitable nonmagnetic media to disperse the …

New Organic/Inorganic Hybrid Sol-Gel Nanocomposite Materials For Raman Gain In Fiber Optics, Stephen James Andrasik

Electronic Theses and Dissertations

The recent increased availability of additional wavelengths in the telecommunications window of about 1300-1600 nm has generated an interest in new optical materials and devices that can operate outside the normally used regions of 840 nm, 1310 nm, and 1550 nm. Specifically, methods to amplify fiber optical data transmission in the regions where there is limited or no existing methods to achieve amplification is of interest in the chemistry and photonic communities. Raman gain is one method that has been proposed to passively amplify optical data transmission through a distributed process. Amplification is obtained through a nonlinear light scattering process …

The Use Of Pyrosequencing For The Analysis Of Y Chromosome Single Nucleotide Polymorphisms, Jeremy Charles Fletcher

Electronic Theses and Dissertations

The potential value of the Y chromosome for forensic applications has been recognized for some time with the current work dedicated to Short Tandem Repeat analysis and Single Nucleotide Polymorphism (SNP) discovery. This study examined the ability of two different SNP analysis methods to determine if they could be utilized in forensic applications and ultimately be developed into an established system for Y chromosome SNP analysis. This study examined two principle SNP analysis systems: single base extension and Pyrosequencing. Pyrosequencing was determined to be superior to single base extension, due to the wealth of information provided with sequencing and the …

Tuning Polymeric Chiral Surfactants For Enhanced Enantiomeric Recognition In Micellar Electrokinetic Chromatography, Jepkoech Tarus

LSU Doctoral Dissertations

The research presented in this dissertation involves the synthesis, modification, characterization, and the application of polymeric surfactants in micellar electrokinetic chromatography (MEKC). Sodium undecenoyl-L-Leucinate (L-SUL) was synthesized and modified by use of alkali metal counterions, alcohols, and Triton X-102. Characterization of the modified poly-L-SUL was performed in order to elucidate the structural changes on the surfactants by use of four techniques. While surface tensiometry was used for the determination of the critical micelle concentration (cmc), fluorescence measurements were used for the determination of the polarity of the modified polymeric surfactants. The information about the size of the polymeric surfactants was …

Investigation Of Structure-Property Relationships Of Heavy-Fermion Materials, Robin Macaluso

LSU Doctoral Dissertations

This work focuses on how local structural features influence large effective masses, magnetism, and superconductivity that are yet to be understood in heavy-fermion materials. Three sets of structurally-related materials are discussed in light of dimensionality, layering effects, choice of transition metal, coordination, and structural distortions: LnnMIn3n+2 (Ln = La, Ce; n = 1, 2, ‡; M = Co, Rh, Ir), CePdGa6, and Ce2PdGa12, and CeNiSb3. The LnnMIn3n+2 (n = 1, 2, ‡; Ln = La, Ce; M = Rh, Ir) intergrowth homologous series presents a unique opportunity to study structure-property relationships. LnnMIn3n+2 (Ln = La, Ce; n = 1, 2; …

Protein Aggregation Studies: Inhibiting And Encouraging Β-Amyloid Aggregation, Jed Paul Aucoin

LSU Doctoral Dissertations

This work demonstrates peptide-based aggregation mediation of fibril forming peptides, notably β-amyloid (1-40), Aβ_1-40. To achieve the goals of this work, Aβ_1-40 aggregation was governed by ionic strength, temperature, and pH. After controlling and reproducing Aβ_1-40 aggregate formation (fibrils), each peptide-based aggregation mediator was evaluated for its ability to self-aggregate and to possess surface-active properties. The incorporation of these mediators in Aβ_1-40 solutions changed the surface tension and produced aggregate complexes of mediator and Aβ_1-40. Evidence that Aβ_1-40 fibril formation may be mediated by disorder-to-order transitions has been observed by layer formation …

Applications Of The Titanium Catalyzed Cyclocarbonylation Towards Natural Product Syntheses, Jongtae Yang

LSU Doctoral Dissertations

Recently an efficient methodology, a hetero Pauson-Khand reaction, based on titanium-catalyzed cyclocarbonylation of tethered enals for the general preparation of ¥ã-butyrolactone rings, which are typically embedded in polycyclic systems of many natural products was reported. To demonstrate this new strategy, the total syntheses of the natural products asteriscanolide and ginkgolide were investigated. The first part of this work is dedicated to synthetic efforts toward the total synthesis of asteriscanolide. Approaches highlighted by the [2,3]-Wittig rearrangement, the thermal silyloxy-Cope rearrangement, and a titanium-catalyzed cyclocarbonylation, which is the pivotal step to afford the ¥ã-butyrolactone ring. This study firmly established the utility of …

Microelectrophoresis System Utilizing Conductivity Detection Analyzing Biological Molecues, Michelle Galloway

LSU Doctoral Dissertations

Microfabrication technology has proven to be a valuable tool for creating polymer-based devices utilized in chemical and biochemical assays. Although, reducing the size of the device allows for short analysis times and reduces the reagent demand to ultrasmall volumes (< 1 nanoliter), a resulting consequence is the constraint placed on the limits of detection associated with the detector hardware required for readout. To overcome such constraints, laser-induced fluorescence (LIF) is often employed as a detection method as it provides low detection limits, which approach the single molecule level. Unfortunately, most LIF systems do not offer the benefits of miniaturization, with the detector components (i.e. laser, optics, filters) often times requiring a much larger footprint compared to the device. Another readout strategy that has shown promise for these devices is conductivity detection. Detection can be accomplished using either conventional-size or microfabricated electrodes, which can be integrated on the device. Although conductivity has been commonly used to detect inorganic or small organic species, the potential for detection of biological species has received little attention. In this work, an integrated conductivity detector was developed for the analysis of amino acids, peptides, proteins, and oligonucleotides (double-stranded DNA). Using the detector, mass detection sensitivities in the range of 10^-18 - 10^-21 moles were achieved. To increase the throughput of the system a state-of-the-art, multichannel device with a conductivity array detector was devised. This device, which consists of a 16-channel fluidic network and a printed circuit board, is geared toward automating three-processing steps onto a single fluidic platform including purification, preconcentration and detection for downstream parallel processing.

The Synthesis And Characterisation Of Diiron And Triiron Carbonyl Cluster Compounds With Sulphur And Phosphine Ligands, Geraldine Gray

Theses

This work is primarily concerned with the synthesis and characterisation of di and triiron carbonyl cluster derivatives which contain sulphur and phosphine ligands.

The first chapter is a review of the literature of such complexes. Included are diiron carbonyl clusters which contain phosphine ligands, those which contain sulphur, and those that contain phosphine and sulphur ligands. Triiron carbonyl clusters which contain phosphine ligands, sulphur ligands and both are also discussed.

Chapter two describes the synthesis of compounds of the type [{Fe₂(SR)₂(CO)₅)₂Ph₂P (CH₂)_nPPh₂] (R = …

Development Of Electrochemical Sensors For Monitoring Glucose, Michael Nesbitt

Theses

The thesis focuses on evaluating calcium alginate as an immobilisation matrix for the oxidase enzyme glucose oxidase for the amperometric determination of glucose. The basic principles of enzymology and enzyme immobilisation is discussed followed by a review of a variety of first, second and third generation type enzyme electrodes. Amperometry as governed by the Cottrell equation and mass transfer models relating to amperometric electrodes are also considered.

Bovine serum albumin (BSA / GOx) enzyme electrode system was employed as a model to evaluate a calcium alginate immobilisation technique for glucose oxidase. The principal methods employed for enzyme immobilisation were:

• …

Synthesis And Characterization Of Polyimide Residuum, Friable Balloons, Microspheres And Foams, Erik Saul Weiser

Dissertations, Theses, and Masters Projects

In order to meet requirements of future NASA systems for advanced polymeric cellular materials, research was undertaken to develop the next generation of polyimide foams which could be utilized as a reusable structural insulation on future Reusable Launch Vehicle (RLV) Programs. This research activity focused on developing polyimide foam and foam structures which were made using monomeric solutions or salt solutions formed from the reaction of a dianhydride and diamine dissolved in a mixture of foaming agents and alkyl alcohols. This process produced a precursor solid residuum which could then be manufactured into foams, friable balloons and microspheres. Polyimide foams …

Binding Studies On Molecularly Imprinted Polymers, Lucy Yue Hu

Dissertations, Theses, and Masters Projects

Molecular imprinting is a rapidly developing technique for preparation of polymeric materials that are capable of molecular recognition for selective separation and chemical identification. to prepare molecularly imprinted polymers (MIPs), a functional monomer and a crosslinker are polymerized in the presence of a template molecule. Then the template is extracted leaving sites which are complementary in both shape and chemical functionality to those of the template. This resin then becomes capable of selectively absorbing the template species. Because of MIPs' stability, predesigned selectivity, and easy preparation, they have been used for separation, sensor, drug development and directed synthesis.;In this study, …

Solid State Nmr Characterization Of Conductive Polyanilines, Yanina Anatolievna Goddard

Dissertations, Theses, and Masters Projects

Different forms of ring deuterated polyaniline with different conductivity have been characterized by solid state deuteron nuclear magnetic resonance.;Quadrupole echo (QE) spectra of all forms of polyaniline consist of a superposition of lineshapes for nearly rigid aromatic rings and a small fraction of rings which undergo fast 180?? flips. The intensity of the fast flipping component is temperature dependent and different for conductive emeraldine salt (ES) and non-conductive emeraldine base (EB). This is a manifestation of the different structure and morphology of these polymers.;Simultaneous measurements of QE lineshapes and the relaxation time anisotropies allowed an accurate description of motion in …

Physiology And Biochemistry Of Sclerotinia Sclerotiorum, A Fungal Plant Pathogen, Erastus Gatebe

Masters Theses

No abstract provided.