Physical Sciences and Mathematics Commons^™

Design And Synthesis Of Beta-Hairpin Peptidomimetics For Modulating Integrin Mediated Cell Adhesion, Abeta Fibrillogenesis And P53-Mdm2 Protein-Protein Interactions, Priyesh Jain

USF Tampa Graduate Theses and Dissertations

Inhibiting therapeutically important protein-protein interactions has been a tremendous challenge for medicinal chemists. The folded 3D structures of peptides and proteins, mainly comprise secondary structural elements i.e α-helices and β-sheet have created an opportunity to design small molecules and peptidomimetic inhibitors of protein-protein interaction (PPI). Hence, information about the formation and stabilization of these secondary structures is vital for designing future drugs. In this dissertation, several cyclic beta-hairpin peptidomimetics that mimic the recognition surface have been designed and synthesized as inhibitors for different targets such as integrin mediated extracellular matrix -cell adhesion in multiple myeloma, p53-MDM2 PPI, amyloid beta fibrillogenesis …

Corrole Synthesis And Catalytic Applications Toward Cobalt(Iii)-Catalyzed Epoxidation, N-H Insertion, And Cyclopropanation, Chung Sik Kim

USF Tampa Graduate Theses and Dissertations

A variety of bromocorroles, useful precusors for Pd-based cross coupling, were sucessfully synthesized in moderate to good yields. Chiral corroles were also synthesized through use of chiral amides in the aforementioned cross coupling reactions. Cobalt complexes bearing π-acceptor (CNtBu) and σ-donor (PPh3) ligands were also prepared in excellent yields. In this dissertation, cobalt (III) corrole complexes were applied to three different reaction areas: epoxidation, N-H insertion, and cyclopropanation. Cobalt(III) corroles were found to be efficient catalysts for epoxidation reactions. The epoxidation reactions can be carried out using ethyl phenyldiazoacetate, an acceptor/donor diazo compound, as a carbenoid precusor.The reaction provided highly …

Strategies To Resolve The Three-Dimensional Structure Of The Genome Of Small Single-Stranded Icosahedral Viruses, Eduardo Sanz Garcia

Theses and Dissertations

The aim of this study is the three-dimensional structural characterization of the genome packaging inside viral capsids via cryo-electron microscopy and three-dimensional reconstruction. The genome of some single-stranded viruses can be densely packaged within their capsid shells. Several stretches of the genome are known to adopt stable secondary structures, however, to date, little is known about the three-dimensional organization of the genome inside their capsid shells. Two techniques have been developed to facilitate the structural elucidation of genome packaging: the asymmetric random-model method, and the symmetry-mismatch, random model method. Both techniques were successfully tested with model and experimental data. The …

The Correlation Of The Concentration Of Selected Metals Determined In Water And Fish Samples From A Public Pond., Paula Kay Edwards

Electronic Theses and Dissertations

The concentrations of heavy metals (Cd, Cu, Fe, Ni, Pb, Zn) were measured in water, and fish samples caught from the pond at Fishery Park in Unicoi County, TN. The water samples were collected once a week for 8 weeks. The amounts of metals in the muscle tissues, gill, and liver of the two fish species were measured. This was to determine if any correlation exists between the metal contents in water and those in the fish samples. The concentration ranges for the heavy metals found in the water samples are as follows: Zn 0.04-0.13; Cu, 0.00-0.00; Pb, 0.00-0.59; Cd, …

Conjugate Additions And Transposition Of The Allylic Alcohols Of Enol Ethers Of 1, 2-Cyclohexanedione., Barnabas Otoo

Electronic Theses and Dissertations

A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one …

Extraction And Determination Of A Selected Polyphenol From Selected Red And Black Grapes By High Performance Liquid Chromatography., Summer Nicole Niles

Undergraduate Honors Theses

Polyphenols are a group of compounds found naturally in plants and they provide much of the flavor, color, and taste to fruits, vegetables, seeds, and other parts of the plants They also act as antioxidants which provide numerous health benefits by protecting cells against damage caused by free radicals. Their antibacterial, anti-inflammatory and anti-allergenic properties have also contributed to the prevention of degenerative diseases, such as cardiovascular diseases and cancers by slowing the rate of oxidative stress on cells. This study was aimed at the identification and quantitation of a specific polyphenol, quercetin, found in grapes commonly purchased at grocery …

Role Of Amyloid Beta Assembly State In The Human Immune Response, Deepa Viswanathan

Dissertations

Alzheimer’s disease (AD) is a slowly progressing neurodegenerative disease that leads to dementia. Histopathological hallmarks that characterize AD are senile plaques formed by extracellular deposition of Amyloid beta (Aβ) peptide and intracellular aggregates of hyperphosphorylated tau protein. The plaques, which are found in the brain parenchyma, comprise both 40 and 42 residue Aβ. Aggregation of Aβ is an established pathogenic mechanism in AD, but little is known about the initiation of this process in vivo. Several studies have revealed significant inflammatory markers such as activated microglia and cytokines surrounding the plaques. Plaques are a hallmark of AD, but they are …

Sequence-Specific And Conformation-Specific Targeting Of Duplex And Quadruplex Dna Grooves With Small Molecules, Rupesh K. Nanjunda

Chemistry Dissertations

Small molecule mediated chemical intervention of biological processes using nucleic acid targets has proven extremely successful and is continually providing exciting new avenues for the development of anti-cancer agents and molecular probes. Among the alternative DNA confrormations, G-quadruplexes has certainly garnered much recognition due to increase in evidences supporting their involvement in diverse biological process. The grooves of the quadruplexes offer an alternate recognition site for ligand interactions with potentially higher selectivity than the traditional terminal stacking sites. DB832, a bifuryl-phenyl diamidine, was recently reported to selectively recognize human telomeric G-quadruplex, as a stacked species, with significant selectivity over duplex …

Chemical Vapor Deposition Of Silanes And Patterning On Silicon, Feng Zhang

Theses and Dissertations

Self assembled monolayers (SAMs) are widely used for surface modification. Alkylsilane monolayers are one of the most widely deposited and studied SAMs. My work focuses on the preparation, patterning, and application of alkysilane monolayers. 3-aminopropyltriethoxysilane (APTES) is one of the most popular silanes used to make active surfaces for surface modification. To possibly improve the surface physical properties and increase options for processing this material, I prepared and studied a series of amino silane surfaces on silicon/silicon dioxide from APTES and two other related silanes by chemical vapor deposition (CVD). I also explored CVD of 3-mercaptopropyltrimethoxysilane on silicon and quartz. …

Activation Of Propargylic Alcohols By Piano-Stool Ruthenium Complexes Bearing Phosphoramidite Ligands, Stephen Andrew Costin

Dissertations

Various piano-stool ruthenium complexes bearing phosphoramidite ligands have been synthesized and characterized spectroscopically and in some cases structurally. Reaction of phosphoramidite ligands with an appropriate metal precursor gives new piano-stool ruthenium complexes [RuCl(L)(arene)(phosphoramidite)], where L = Cl, PPh3, or others. The novel complexes are tested for their ability to activate propargylic alcohols catalytically as well as stoichiometrically. Specifically, catalytic substitution of propargylic alcohols via allenylidene intermediates is envisioned. Stoichiometric reactions designed to form stable, isolable allenylidenes are sought as well. h6-p-cymene complexes of the type [RuCl2(h6-p-cymene)(phosphoramidite)] activate propargylic alcohols in the reaction with carboxylic acids to form b-oxo esters. The …

Study Of 3,3' Vs. 4,4' Dds Isomer Curatives On Physical Properties And Phenyl Ring Motions Of Dgeba Epoxy Via Molecular Dynamics, Deuterium Nmr, And Dielectric Spectroscopy, Samuel James Tucker

Dissertations

The purpose of this research is to develop a multiscale understanding of crosslinked amorphous matrices, connecting molecular level events to macroscopic properties. To accomplish this goal, our methodology was to identify network architectures that influence molecular level energy dissipation through mechanisms such as bond rotations, torsions, and ring flips and then relate those molecular motions to macroscopic properties. Studies were accomplished on two aerospace grade matrices: the epoxy, diglycidyl ether of bisphenol A (DGEBA) cured with two amines, 3,3’- diaminodiphenyl sulfone (33DDS) and 4,4’-diaminodiphenyl sulfone (44DDS). The 33DDS/DGEBA and 44DDS/DGEBA served both to provide a baseline for experimental testing of …

Novel Electrochemical Detections Of Biologically And Environmentally Relevant Substances, Clarissa E. Tatum

Doctoral Dissertations

Development and studies of new electrochemical methods for the detection of various biologically and environmentally relevant substances are the focus of this dissertation. A dual amperometric sensor, capable of the simultaneous, real-time determination of NO and O,2, has been developed and optimized. Many tests were performed in order to reduce cross-talking between the two sensors, and an electro-deposited polymer, poly-5-amino-1-naphthol, was shown to reduce the cross-talking to insignificant levels. The use of bismuth-based electrodes in the detection of various metals has been explored. A bismuth bulk electrode has been developed, optimized, and used for the individual and simultaneous determination of …

Tantalum Carbene And Imide Complexes. Synthesis, Characterization, And Pathways Of Formation, Julia Kathryn Covington Abbott

Doctoral Dissertations

This dissertation focuses on two different types of organometallic compounds, carbenes and imides. The first project deals with the archetypal Schrock carbene, and the second project studies complexes that contain metal-nitrogen bonds, both amides and imides.

A summary of the research in this dissertation is discussed in Chapter 1. Chapter 2 begins the studies of the archetypal Schrock carbene (Bu^tCH₂)₃Ta=CHBu^t. The studies include the synthesis of deuterated compounds (Bu^tCD₂)₃TaCl₂ and Bu^tCD₂Li, observation and identification of the intermediate, Ta(CD₂Bu^{t …}

The Importance Of Chain Connectivity In The Formation Of Non-Covalent Interactions Between Polymers And Single-Walled Carbon Nanotubes And Its Impact On Dispersion, Dias Linton

Doctoral Dissertations

Polymer nanocomposites have garnered incredible promise in the field of material science due to the excellent mechanical strength, thermal and electrical conductivities of the nanoparticles and the extension of these properties to the processing flexibility inherent to plastics. However, practical realization of these nanoparticle-based materials has been hindered by the tendency of these nanoparticles to aggregate as a result of strong inter-particle forces. In this dissertation, we investigate the formation of non-covalent charge transfer interactions between polymers and single-walled carbon nanotubes (SWNTs) with the goal of optimizing interfacial adhesion and homogeneity of nanocomposites without modifying the SWNT native surface.

Nanocomposites …

Speciation And Spectroscopy Of The Uranyl And Tetravalent Plutonium Nitrate Systems: Fundamental Studies And Applications To Used Fuel Reprocessing, Nicholas A. Smith

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation explores the use of UV-Visible spectroscopy and Time Resolved Laser Induced Fluorescence spectroscopy as near real time process monitors of uranium and plutonium concentrations in aqueous reprocessing trains. The molar absorptivities and linear ranges of these metals were investigated under total nitrate and acid concentrations similar to those found in current reprocessing systems. Concurrent to this, a new multiple wavelength monitor was derived that is capable of determining the total nitrate concentration spectroscopically. This method uses the uranium absorbance spectrum to calculate the nitrate concentration in solution. When used as part of an Advanced Safeguard suite, this technique …

Chemical And Electronic Structure Of Surfaces And Interfaces In Compound Semiconductors, Sujitra Pookpanratana

UNLV Theses, Dissertations, Professional Papers, and Capstones

The interface formation between two different materials is important in applications for optoelectronic devices. Often, the success or performance of these devices is dependent on the formation of these heterojunctions. In this work, the surface and interfaces in such materials for optoelectronic devices are investigated by a suite of X-ray analytical techniques including X-ray photoelectron (XPS), X-ray excited Auger electron (XAES), and X-ray emission (XES) spectroscopies to provide novel insight.

For the group III-nitrides (e.g., AlxGa1-xN) used in many light emitting devices, a significant challenge exists to form an Ohmic contact. The electron affinities and band gaps of GaN and …

Synthesis And Electrical Properties Of Functional Block Copolymer/Inorganic Nanocomposite Materials, Hongying Chen

Dissertations

Sulfonated poly[styrene-b-ethylene-co-butylene-b-styrene] (sSEBS) block copolymers/inorganic nanocomposite materials were synthesized via in situ formation of inorganic fillers and characterized particularly for their dielectric properties and proton conductivities.

In preparation of sSEBS/SrTiO₃ nanocomposites, titanium (IV) isopropoxide [Ti(OPrⁱ)₄] complex was diffused into sSEBS film, followed by subsequent hydrolysis of [Ti(OPr i)4], diffusion of strontium cations in sSEBS domains, and in situ formation of crystalline SrTiO₃. sSEBS with sulfonation degree of 38.1% and 65.0% were employed, and relevant sSEBS/SrTiO₃ composites contain SrTiO₃ of 10-15 wt%. Elemental composition characterization with ESEM/EDX indicated uniform distribution of …

The Influence Of Nanoporous Crystalline Structure On Low Molecular Weight Mass Transport In Syndiotactic Polystyrene, Justin Paul Brandt

Dissertations

Solid-state structure, crystalline morphology, crystallization kinetics, thermal, free volume, and gas transport properties of semicrystalline syndiotactic polystyrene (sPS) and ethylene vinyl alcohol copolymers (EVOH) have been investigated. Solid-state structure of sPS after crystallization from the melt and glassy state was examined by differential scanning calorimetry (DSC), density and wide angle x-ray diffraction analysis (WAXD). The measurements confirmed low density of syndiotactic polystyrene crystalline forms, which in the case of α and δe was smaller and in the case of β and γ crystalline forms was slightly larger than the density of the glassy amorphous sPS. Positron annihilation lifetime spectroscopy (PALS) …

Folate Receptor-Targeted Delivery Of Small Interfering Rna To Cancer Cells, Yilin Zhang

Dissertations

The vitamin folic acid (folate, FA) has been extensively explored as a targeting ligand to deliver a variety of diagnostic/prognostic/therapeutic agents into various tumors through the assistance of its receptor – the folate receptor (FR). FR is over-expressed in many types of human cancer and can mediate internalization of FA-conjugates through an endocytic pathway. The discovery of small interfering RNA (siRNA), which is cable of inducing potent gene silencing in a sequence-specific manner, provides an excellent molecular tool to suppress aberrant gene expression in malignancies, and therefore siRNA has the potential to revolutionize cancer therapeutics. Towards the goal of developing …

Design And Regioselective Synthesis Of Two And Three-Pronged C60 Fullerene Derivatives And Their Applications In Molecular Electronics, Angy Ortiz-Hernandez

All Dissertations

Since the introduction of semiconductors in the second half of the 20th century, advancements in electronics and technology have been tremendous. In particular, the rapid development of silicon-based computer chip technology and miniaturization of electronic components has been tremendous. Since silicon-based materials have a limit in terms of size, scientists proposed that individual molecules could behave as single electronic components for high degree of miniaturization.
Given that the molecules of interest must have dimensions on the nanometer scale, be able to bind to the electrode surface and have electron donor-acceptor properties, C₆₀ fullerene has been a prime candidate for …

Novel Neomycin Conjugates For Multi-Recognition Of Nucleic Acids, Albert Willis

All Dissertations

Neomycin is an aminoglycoside antibiotic known for its high affinity for RNA duplex structures. Recent developments from our labs have indicated that aminoglycoside binding is not limited to RNA, but to nucleic acids that, like RNA, adopt conformations similar to A-form. Our group sought to further expand the utility of aminoglycoside binding to B-DNA structures by conjugating neomycin, an aminoglycoside antibiotic, with the B-DNA minor groove binding ligand Hoechst 33258. Envisioning a dual groove-binding mode, we have extended the potential recognition process to include a third, intercalative moiety. Furthermore, we observe remarkable recognition of such conjugates with RNA duplex. Spectroscopic …

Biochemical Characterization Of Theromin, A Novel Leech Inhibitor, And The Interaction Between The Fourth Metalbinding Domain Of Wilson Disease Protein And Its Copper(I) Chaperone Hah1, Brian A. Zeider

Dissertations

Theromin, a novel thrombin inhibitor from the leech Theromyzon tessulatum, has been shown to be the strongest inhibitor to date. There has been a lot of attention on direct thrombin inhibitors as a much more efficient drug for anticoagulation therapy. One main reason for the need of strong direct thrombin inhibitors is that the current therapy, heparin, causes alternative clotting events in some patients where antibodies are made to the heparin/thrombin complex and causes clots to occur by different methods. Recently there has been a strong inhibitor from a leech used, hirudin, that can inhibit with a K_{i …}

Synthesis And Optical Properties Of Silver Nanostructures, John Heckel

All Dissertations

Silver nanoparticles interact with light via the excitation of plasmon resonances that are the collective oscillations of the free electron density. This excitation represents the most efficient mechanism for the interaction of light with matter and therefore the nanoparticles are of great interest for both fundamental and practical points of view. In the following dissertation, silver nanoparticles, core-shell nanoparticles, and silver nanoparticle clusters were synthesized and there optical properties were investigated.
Chapter 1 contains general background information about the optical properties of bulk and silver nanoparticles. It also contains a concise description of two of my collaborative projects that did …

Synthesis Of Trimetallic Nitride Endohedral Metallofullerene Derivatives For Enhanced Solar Energy Conversion, Julio Pinzon Joya

All Dissertations

The preparation and electrochemical properties of donor - acceptor systems based on trimetallic nitride endohedral metallofullerenes (TNT-EMFs) for enhanced solar energy conversion is described. It was found that TNT-EMFs have an enhanced ability to stabilize charge separated states formed upon light irradiation when compared to empty cage fullerene analogues. The influence of the linker connecting the donor and acceptor moieties was studied in two different systems. Optimal conditions for preparing cyclopropanated Bingel-Hirsch derivaties of the most common TNT-EMFs were found; this functionalization approach is a very useful alternative to the 1,3-dipolar cycloaddition reactions that yield pyrrolidine derivatives, because the latter …

Redox-Magnetohydrodynamic (Mhd) Microfluidics: Fundamentals, Optimization, And Applications To Analytical Chemistry, Melissa Christine Weston

Graduate Theses and Dissertations

Microfluidic systems are of great interest in analytical chemistry for the development of lab-on-a-chip devices. This dissertation describes fundamental investigations of magnetohydrodynamics with added redox species (redox-MHD) as a new microfluidic approach for use in analytical applications. Redox-MHD is attractive because it offers a unique combination of desirable features that are otherwise only available separately with individual micropumps. Redox-MHD is compatible with aqueous and nonaqueous solutions, does not require moving parts, easily reverses flow direction, and requires only low voltages. An ion flux is generated from the oxidation or reduction of an electroactive species at specific locations by activated electrodes …

The Synthesis, Characterization, And Electrochemical Study Of Tris(Pyrazolyl)-Type Iron(Ii) Complexes, Iron(Ii) Sulfur- And Selenium-Containing Complexes, And Tris(Pyrazolyl)-Type Ruthenium(Ii) Complexes, Christopher Underwood

All Theses

Highly reactive radical species such as hydroxyl radical cause oxidative stress, resulting in chronic or degenerative diseases. In the biological Fenton reaction, iron(II) generates hydroxyl radical, OH, but only within a specific electrochemical potential window (-324 mV to 640 mV). Selenium and sulfur compounds have been extensively studied for their antioxidant properties, and they may exert their effects by binding iron(II) and shifting its electrochemical potential out of this window. This work has investigated the synthesis and electrochemical characterization of iron(II) chalcogenate complexes and iron(II) chalcogenone complexes. Cyclic voltammetry (CV) of [Fe(EPh)4][(PPh4)2] (E = S, Se) complexes shows Fe2+/3+ redox …

The Removal Of Wood Components From Hardwood By Hot Water, Rory Jara

Electronic Theses and Dissertations

Hot-water extraction of hemicelluloses from wood is a promising technology in the integrated biorefmery concept. A particular case is where the pulp industry makes co-products such as ethanol and acetic acid besides pulp thereby maximizing the value of biomass. Similarly, the oriented strand board (OSB) industry appears to be suitable for this technical approach as it is composed of large centralized facilities. Many studies have been carried out on the kinetics and mechanism of hot-water extraction of lignocellulosics. However, most of these studies were performed in batch reactors which are not best suited to determine intrinsic kinetics of hemicellulose dissolution …

Conceptual Model Testing And Development For Neptunium And Radium Sorption To Srs Sediments, Todd Miller

All Theses

Models which can estimate environmental transport of contaminants are required to ensure minimal risk to the public. These models require accurate transport parameters in order to correctly predict how these contaminants will move in the subsurface. This work aimed to determine more accurately the distribution coefficients for neptunium, strontium, and radium for the Savannah River Site (SRS) Performance Assessment (PA). All neptunium sorption studies were performed at a pH value of 5.50 and an ionic strength of 0.01M as NaCl with neptunium concentrations ranging from 0.01 to 50 ppb. Two different sediments were examined, SRS Subsurface Clayey and SRS Subsurface …

Preparation And Studies Of Fluorescent Carbon Nanomaterials, Xin Wang

All Dissertations

There have been rapid advances in the development and applications of semiconductor quantum dots (QDs) represented by CdSe/ZnS. However, a serious limitation of these QDs is the necessary use of toxic heavy metals. Fluorescent 'carbon dots' (surface passivated carbon nanoparticles) are developed as alternative to classical semiconductor QDs.
The carbon dots could be made to be highly fluorescence, with emission quantum yields close to 60%. Their optical properties resemble bandgap transitions found in nanoscale semiconductors, suggesting that carbon particles at the nanoscale acquire essentially semiconductor-like characteristics.
The fluorescence in carbon dots could be quenched efficiently by electron acceptor or donor …

Spectral Reflectance As An Indicator Of Foliar Concentrations Of Arsenic In Common Sunflower (Helianthus Annuus), Yuridia Patricia Peralta De Gandy

Theses and Dissertations - UTB/UTPA

Studies were conducted to investigate the use of spectral reflectance by foliage of common sunflower as a potential indicator of arsenic contamination of soil. Germination method was developed for sunflower seeds, and cohorts of sunflower seedlings in hydroponic tanks were established. The cohorts were exposed to 0 ppm, 5 ppm, 7.5 ppm, and 10 ppm treatments of As (V) and reflectance measurements of foliage were collected using a spectroradiometer during two experiments.Results demonstrated the feasibility of using spectral reflectance by foliage of common sunflower as a potential indicator of arsenic contamination. In both experiments, arsenic concentrations in leaf tissues were …