Chemistry Commons^™

Investigations Of S-Glutathionylation Of Brain Proteins In The Progression Of Alzheimer's Disease And Of A Potential Glutatione Mimetic As A Treatment Of Alzheimer's Disease, Shelley Faye Newman

University of Kentucky Doctoral Dissertations

Alzheimer’s disease (AD) is a neurodegenerative disorder characterized by neurofibrillary tangles, senile plaques and loss of synapses. Many studies support the notion that oxidative stress plays an important role in AD pathogenesis. Previous studies from our laboratory employed redox proteomics to identify oxidatively modified proteins in the AD inferior parietal lobule (IPL). The proteins were consistent with AD pathology and have been central to further investigations of the disease. The present study was focused on the identification of specific targets of protein S-glutathionylation in AD, early AD (EAD), and mild cognative impairment (MCI) using a redox proteomics approach. In AD …

Imide-Functionalized Conjugated Polymers: Synthesis, Structure-Property And Device Studies, Xugang Guo

University of Kentucky Doctoral Dissertations

Organic semiconductors are widely studied as potential active components for consumer electronics due largely to their easily tuned properties and the promise of lower-cost solution-based processing technology. Imide-functionalized organic small molecule compounds have been one of the more important and studied organic semiconductors. However, very few imide-functionalized conjugated polymers have been reported in the literature. The body of this dissertation focuses on the synthesis, structure-property and device studies of imide-functionalized conjugated polymers. Reasons for choosing arylene imides as polymer building blocks include: a) they impart low-lying LUMOs to polymers, allowing band-gap engineering through choice of comonomers with variable electron-donating ability; …

Use Of Boron Compounds To Precipitate Uranium From Water, David A. Atwood

Chemistry Faculty Patents

A method is provided for removing uranium from water. The method includes the mixing of a boron reagent with water contaminated with uranyl dication ions, leading to removal of the uranium from that water.

Tetrahymena Thermophila And Candida Albicans Group I Intron-Derived Ribozymes Can Catalyze The Trans-Excision-Splicing Reaction, P. Patrick Dotson Ii, Ashley K. Johnson, Stephen M. Testa

Chemistry Faculty Publications

Group I intron-derived ribozymes can catalyze a variety of non-native reactions. For the trans-excision-splicing (TES) reaction, an intron-derived ribozyme from the opportunistic pathogen Pneumocystis carinii catalyzes the excision of a predefined region from within an RNA substrate with subsequent ligation of the flanking regions. To establish TES as a general ribozyme-mediated reaction, intron-derived ribozymes from Tetrahymena thermophila and Candida albicans, which are similar to but not the same as that from Pneumocystis, were investigated for their propensity to catalyze the TES reaction. We now report that the Tetrahymena and Candida ribozymes can catalyze the excision of a …

Inversion Symmetry And Local Vs. Dispersive Interactions In The Nucleation Of Hydrogen Bonded Cyclic N-Mer And Tape Of Imidazolecarboxamidines, Sihui Long, Venkatraj Muthusamy, Peter G. Willis, Sean Parkin, Arthur Cammers

Chemistry Faculty Publications

Substitutional changes to imidazolecarboxamidine that preserved intermolecular hydrogen bonding in the solid state were used to study the relationship between packing and the hydrogen bond motif. Various motifs competed, but the most common imidazolecarboxamidine crystalline phase was a C_i symmetric dimer that established inversion centers by associating enantiomeric tautomers. Counter to intuition, the calculated gas-phase energies per molecule of the solid state atomic coordinates of the C_i dimer motifs were higher than those of the C₁ dimer, trimer, tetramer and tape motifs, while the packing densities of C_i dimers were found to be higher. This result …

Silylethynylated Heteroacenes And Electronic Devices Made Therewith, John E. Anthony, Marcia M. Payne, Susan A. Odom, Sean Parkin

Chemistry Faculty Patents

Novel silylethynylated heteroacenes and electronic devices made with those compounds are disclosed.

Aequorin And Obelin Mutants With Differing Wavelengths And Bioluminescence, Sylvia Daunert, Sapna K. Deo, Emre Dikici, Laura Rowe

Chemistry Faculty Patents

The invention relates to aequorin and obelin mutants whose emission is shifted with respect to wild type. The shift in emission is accomplished using a combination of mutations of amino acids within aequorin or obelin that affect bioluminescence; use of different types of chromophores, i.e., coelenterazines with variable emission characteristics; and modifications of the photoprotein with fluorophores that will allow for emission of light at longer wavelengths as a result of energy transfer. Additionally, an assay employing aequorin mutants to test for HIV-1 protease inhibitors is disclosed.

Syntheses, Structures And Magnetic Characterization Of Di- And Trivalent Hydridotris(3,5-Dimethylpyrazol-1-Yl)Borate Cyanomanganates, Minao Tang

University of Kentucky Master's Theses

The syntheses, structures, and magnetic properties of a series of di/trivalent hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) cyanomanganates were investigated. Treatment of manganese(III)acetylacetonate with KTp* followed by tetra(ethyl)- ammonium cyanide affords [NEt₄][(Tp*)Mn^II(acac)(CN)] (1). Attempts to oxidize 1 with iodine affords {(Tp*)Mn^II(κ²O-acac-CN)}_n (7); a minor complex {[NEt₄][(Tp*)Mn^II(κ²O-acac-3-CN)]₂(µ-CN) (8) was also isolated.

The manganese(II) complex [NEt₄][(Tp*)Mn^II(κ²O-acac-3-CN)(κ¹N -3-NC-acac)] (2) was obtained via treatment of Mn(3-acacCN)₃ with KTp* and [NEt₄]CN. [NEt₄]₂[Mn …

Methods Development In Qualitative And Quantitative Proteomics, Ting Liu

University of Kentucky Doctoral Dissertations

Proteomics based on liquid chromatography coupled to mass spectrometry has developed rapidly in the last decade and become a powerful tool for protein mixtures analysis. LC-MS based proteomics involves four steps, sample preparation, liquid chromatography, mass spectrometry and bioinformatics. Improvements in each step have extended its applications to new biological research areas. This dissertation mainly focuses on method developments in both qualitative and quantitative proteomics.

The first part of this dissertation focuses on qualitative analysis of T. gondii Parasitophorous Vacuole Membrane (PVM) proteins, which is very important for T. gondii’s survival. The hypothesis of this study is that proteomic …

Benzene-1,3-Diamidoethanethiol (Bdeth2) And Its Metal Compounds, Kamruz Md Zaman

University of Kentucky Doctoral Dissertations

There is a global need to find a permanent and readily implemented solution to the problem of heavy metal pollution in aqueous environments. A dithiol compound, benzene-1,3-diamidoethanethiol (BDETH₂), also known as N,N'-bis(2-mercaptoethyl) isophthalamide or N,N'-bis(2-mercaptoethyl)-1,3-benzenedicarboxamide, capable of binding divalent metal ions, has been synthesized and characterized. A broad range of BDET-metal compounds, spanning the periodic chart, has been prepared and characterized by IR, MS, EA, Raman, XAFS and TGA. The characteristics of the BDET-M compounds were determined through secondary reactions. In an effort to derivatize BDET-M compounds through alkylalumination a new cyclic compound, 1,3- bis(4,5-dihydrothiazolo)benzene, has …

Metabolite Analysis Of Clostridium Thermocellum Using Capillary Electrophoresis Based Techniques, Anup P. Thakur

University of Kentucky Doctoral Dissertations

Clostridium thermocellum is a thermophilic bacterium that converts biomass to ethanol directly; however, high sensitivity of this bacterium toward ethanol limits its commercial utility. To elucidate the effect of ethanol on the growth of this bacterium a metabolite analysis of C. thermocellum was performed. The hypothesis of the project was that exogenous ethanol alters the metabolite profile of C. thermocellum. For metabolite analysis, capillary electrophoresis-electrospray ionization-mass spectrometry method (CE-ESI-MS) was developed due to highly polar and charged nature of metabolites. To increase the sensitivity of CE-ESI-MS, several parameters at the ESI interface were optimized. The application of 50% isopropanol …

Regulation Of L-Type Voltage-Dependnet Calcium Channels By The Rem Gtpase, Chunyan Pang

University of Kentucky Doctoral Dissertations

The Rem, Rem2, Rad, and Gem/Kir GTPases, comprise a novel subfamily of the small Ras-related GTP-binding proteins known as the RGK GTPases, and have been shown to function as potent negative regulators of high voltage-activated (HVA) Ca²⁺ channels upon overexpression. HVA Ca²⁺ channels modulate Ca²⁺ influx in response to membrane depolarization to regulate a wide variety of cellular functions and they minimally consist of a pore-forming α1 subunit, an intracellular β subunit, and a transmembrane complex α₂/δ subunit. While the mechanisms underlying RGK-mediated Ca²⁺ channel regulation remain poorly defined, it appears that both membrane …

Carbon Nanotube Supported Metal Catalysts For NoX Reduction Using Hydrocarbon Reductants, Eduardo Santillan-Jimenez

University of Kentucky Doctoral Dissertations

Nitrogen oxides (NO_x) are atmospheric pollutants that pose a serious threat to both the environment and human health. Although catalytic deNO_x technologies for engines working under stoichiometric air-to-fuel ratios (i.e., most gasoline engines) are already available, their performance is unsatisfactory under excess air conditions like those under which diesel engines operate.

The selective catalytic reduction of NO_x with hydrocarbon reductants (HC-SCR) is a potential deNO_xsolution for diesel engines, whose operating temperatures are 150-500 ºC. Given that is unlikely for a single catalyst to show acceptable activity throughout this entire temperature span, the use of …

Mechanistic Investigations Of The Trans Excision-Splicing And Trans Insertion-Splicing Reaction, Perry Patrick Dotson Ii

University of Kentucky Doctoral Dissertations

Group I intron-derived ribozymes are catalytic RNAs that have been engineered to catalyze a variety of different reactions, in addition to the native self-splicing reaction. One such ribozyme, derived from a group I intron of Pneumocystis carinii, can modify RNA transcripts through either the excision or insertion of RNA sequences. These reactions are mediated through the trans excision-splicing (TES) or trans insertionsplicing (TIS) reaction pathways. To increase our current understanding of these reactions, as well as their general applicability, a mechanistic and kinetic framework for the TES reaction was established. Furthermore, additional ribozymes were investigated for their ability to …

Trans-Excision-Splicing Ribozyme And Methods Of Use, Stephen M. Testa, Michael A. Bell

Chemistry Faculty Patents

A group I intron-derived ribozyme which binds RNA in trans, excises an internal segment from within the RNA, and splices the remaining 5′ and 3′ ends of the RNA back together (the trans-excision-splicing reaction) is disclosed. The excised segment can be as long as 28 nucleotides, or more, and as little as one nucleotide. The ribozymes of the invention are easily modified to alter their sequence specificity. Such ribozymes represent a new and potentially powerful class of generally adaptable genetic therapeutics.

Catalytic Cleavage Of Phosphate Ester Bonds By Boron Chelates, David A. Atwood

Chemistry Faculty Patents

Novel chemical compounds are disclosed having the general formula L{YX_m}_n, wherein X is selected from the Group 13 elements, Y is a halide, and L is a chelating ligand containing at least one binding atom contacting the Group 13 element, the atom being selected from the group consisting of C, N, O, and S, and m and n are integers having a value of at least 1. L may be a Schiff base type ligand, such as a salen ligand. The compositions of the present invention may be bidentate, quadridentate, or greater. The compositions may be …

Polymorphism Of Four Enantiotropic Crystalline Systems Containing Ni(Ii), H2O, 15-Crown-5 And No3-, Maxime Andre Siegler

University of Kentucky Doctoral Dissertations

The series of compounds [M(H₂O)₂(15-crown-5)](NO₃)₂, M = Mg, Mn, Co, Cu and Zn, has been extended to include two new phases for M = Fe and two new phases for M = Ni. The system [M(H₂O)₂(15-crown-5)](NO₃)₂ is remarkable for having many high-Z’ phases (Z’ > 1) with similar packing and for having solid-solid phase transitions through which there is no significant loss of crystallinity. The synthesis of the analogous Ni complex was carried out. Single-crystal X-ray diffraction showed …

Nitroreductase: Evidence For A Fluxional Low-Temperature State And Its Possible Role In Enzyme Activity, Peng Zhang

University of Kentucky Doctoral Dissertations

The enzyme nitroreductase (NR) catalyzes two-electron reduction of high explosives such as trinitrotoluene (TNT), a wide variety of other toxic nitroaromatic compounds, as well as riboflavin derivatives, using a tightly-bound flavin mononucleotide (FMN) cofactor. It has important environmental and clinical implications. Previous studies have focused on elucidating NRs catalytic mechanism and solving its crystal structure.

In this dissertation work, we first develop and implement new strategies for labeling NR with stable isotopes, and report a completely re-designed protocol for NRs purification. Then we report the successful assignment of over half of NRs backbone resonances using 3d-NMR methods. The most significant …

Oxidative Dna Damage In Mild Cognitive Impairment And Late-Stage Alzheimer's Disease, Mark A. Lovell, William R. Markesbery

Chemistry Faculty Publications

Increasing evidence supports a role for oxidative DNA damage in aging and several neurodegenerative diseases including Alzheimer's disease (AD). Attack of DNA by reactive oxygen species (ROS), particularly hydroxyl radicals, can lead to strand breaks, DNA–DNA and DNA–protein cross-linking, and formation of at least 20 modified bases adducts. In addition, α,β-unsaturated aldehydic by-products of lipid peroxidation including 4-hydroxynonenal and acrolein can interact with DNA bases leading to the formation of bulky exocyclic adducts. Modification of DNA bases by direct interaction with ROS or aldehydes can lead to mutations and altered protein synthesis. Several studies of DNA base adducts in late-stage …

Cleavage Of Phosphate Ester Bonds By Use Of Novel Group 13 Chelate Compounds, David A. Atwood

Chemistry Faculty Patents

A novel chemical compound has a general formula (LX)_nY wherein X is selected from a group consisting of a group 13 element other than boron, Y is selected from a group consisting of a halide, a chlorate, a sulfate and a nitrate and L is a chelating ligand containing two nitrogen and two oxygen donor groups where n=1 or 2.

Solution And Solid State Interactions Between Ionic Π-Systems, Jing Chen

University of Kentucky Doctoral Dissertations

Although attractive interactions between π systems (π-π interaction) have been known for many years, understanding of its origin is still incomplete. Quantitative measuring of π-stacking is challenging due to the weak nature of the π-π interaction. This dissertation aims at elucidating a quantitative conformational analysis by NMR ring current anisotropy of an organic compound capable of intramolecular π-stacking in solution and studying charge effects on the stacking of π-systems. This dissertation offers four contributions to the area. (1) A general approach to four-state, conformational analysis based on the magnetic anisotropy of molecules undergoing fast dynamic exchange is described. (2) Study …

26Al-Containing Acidic And Basic Sodium Aluminum Phosphate Preparation And Use In Studies Of Oral Aluminum Bioavailability From Foods Utilizing 26Al As An Aluminum Tracer, Robert A. Yokel, Aaron A. Urbas, Robert A. Lodder, John P. Selegue, Rebecca L. Florence

Pharmaceutical Sciences Faculty Publications

We synthesized ²⁶Al-containing acidic and basic (alkaline) sodium aluminum phosphates (SALPs) which are FDA-approved leavening and emulsifying agents, respectively, and used them to determine the oral bioavailability of aluminum incorporated in selected foods. We selected applicable methods from published syntheses (patents) and scaled them down (∼3000- and 850-fold) to prepare ∼300–400 mg of each SALP. The ²⁶Al was incorporated at the beginning of the syntheses to maximize ²⁶Al and ²⁷Al equilibration and incorporate the ²⁶Al in the naturally-occurring Al-containing chemical species of the products. Near infrared spectroscopy (NIR) and X-ray powder diffraction (XRD) were used …

Method For Prevention Of Solid Dissolution Through Covalent Ligand Bonding, David A. Atwood

Chemistry Faculty Patents

Methods for preventing dissolution of solid substrates, such as metal leaching from coal or corrosion of metal surfaces, are provided.

To read the remainder of this abstract, please download this patent.

Studies Of Unusual Packing And Of Polymorphism In Two Crystal Systems, Xiang Hao

University of Kentucky Doctoral Dissertations

Crystal structures of anhydrous pinacol, the hexagonal pinacol, pinacol monohydrate, and pinacol hexahydrate were studied. In all the structures crystal packing is unusual and complicated. The origin of the complexity may be the difficulty in filling space densely and while also satisfying the H-bonding requirements when the molecule has few internal degrees of freedom.

Five 15-crown-5 complexes of M(NO₃)₂ (M = Cu, Zn, Mg, Co, Mn) were synthesized and characterized using X-ray diffraction and differential scanning calorimetry. The system is rich in polymorphs. Nine definite solid-state phases were identified. More phases probably exist in the solid state …

Magnetoelastic Sensor For Characterizing Properties Of Thin-Film/Coatings, Leonidas G. Bachas, Gary Barrett, Craig A. Grimes, Dimitris Kouzoudis, Stephan Schmidt

Chemistry Faculty Patents

An apparatus for determining elasticity characteristics of a thin-film layer. The apparatus comprises a sensor element having a base magnetostrictive element at least one surface of which is at least partially coated with the thin-film layer. The thin-film layer may be of a variety of materials (having a synthetic and/or bio-component) in a state or form capable of being deposited, manually or otherwise, on the base element surface, such as by way of eye-dropper, melting, dripping, brushing, sputtering, spraying, etching, evaporation, dip-coating, laminating, etc. Among suitable thin-film layers for the sensor element of the invention are fluent bio-substances, thin-film deposits …

Substituted Pentacenes And Electronic Devices Made With Substituted Pentacenes, John E. Anthony, David L. Eaton, Sean Parkin

Chemistry Faculty Patents

Novel substituted pentacenes and electronic devices made with those substituted pentacenes are disclosed.

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 …

Dual Stage Microvalue And Method Of Use, Marc J. Madou, Sylvia Daunert

Chemistry Faculty Patents

A micro-machined drug delivery device and method of use for the delivery of labile drugs is disclosed. A micro-machined sensing device and method of use is also disclosed. A micro-machined drug delivery and sensing device and method of use is additionally disclosed. All three devices are intended to be inserted into a patient's body. The drug delivery devices allow for the mixing of drug components prior to the release of the mixture into the patient's body where the mixture is labile. The micro-machined sensing device is suitable for monitoring the concentration of a specific chemical in a patient's body fluids …

Method Of Solubilizing Single-Walled Carbon Nanotubes In Organic Solutions, Robert C. Haddon, Jian Chen

Chemistry Faculty Patents

Naked single-walled nanotube carbon metals and semiconductors are dissolved in various organic solutions.

Multidentate Sulfur-Containing Ligands, David A. Atwood, Brock S. Howerton, Matthew Matlock

Chemistry Faculty Patents

Novel sulfur-containing ligands for binding of heavy metals are disclosed.

To read the remainder of this abstract, please download this patent.