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New Bio-Analytical Separations Utilizing Chiral Mobile Phase Additives In Thin Layer Chromatography And Chiral Stationary Phases In High Performance Liquid Chromatography, Jo Dee Duncan

Doctoral Dissertations

"The problem addressed by this dissertation is the separation of optical isomers in commercial as well as biological samples. The chromatographic separation of enantiomers is an important and rapidly developing field of study. Chiral separations of pharmaceutical compounds and important organic intermediates in high performance liquid chromatography (HPLC) and thin layer chromatography (TLC) were achieved. Two methods were employed for the direct liquid chromatographic resolution of chiral analytes: chiral stationary phases (CSPs) and chiral mobile phase additives (CMAs). Native and derivatized ß-cyclodextrins (ß-CD) were used as chiral stationary phases in reverse phase and normal phase HPLC, respectively. This study marked …

In Situ Infrared Evidence For The Electrochemical Incorporation Of Hydrogen Into Si And Ge, K. C. Mandal, F. Ozanam, J.-N. Chazalviel

Faculty Publications

No abstract provided.

The Cytosolic-Binding Protein For The Immunosuppressant Fk-506 Is Both A Ubiquitous And Highly Conserved Peptidyl-Prolyl Cis-Trans Isomerase, John Siekierka, Gregory Wiederrecht, Heidi Greulich, D. Boulton, Shirley H.Y. Hung, John G. Cryan, P. J. Hodges, Nolan H. Sigal

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

We have recently isolated an abundant cytosolic protein from human T-cells which specifically binds the immunosuppressive agent, FK-506. The FK-506-binding protein (FKBP) is a member of a novel class of proteins possessing peptidyl-prolyl cis-trans isomerase activity. These proteins are believed to play an important role in accelerating the rate at which proteins fold into their native conformations. In the present study, we demonstrate that FKBP is not a lymphoid-specific protein, but is widely distributed and phylogenically conserved. FKBP, purified from three sources (a human T-lymphocyte cell line JURKAT, bovine calf thymus, and Saccharomyces cerevisiae) exhibit identical molecular weights, immunological cross-reactivities, …

Intracellular Degradation Of Ribosomes In A Mesophilic And A Thermophilic Species Of Bacillus, Joe William Davis

Dissertations

The rates of intracellular degradation of ribosomal proteins were compared in a mesophilic and a thermophilic species of Bacillus. Cells were grown under various incubation conditions in the presence of a 14^C-protein hydrolysate m order to label the ribosomes. Rates of ribosome degradation were evaluated in terms of changes in the specific activity of in vivo ribosomes as a function of incubation time. The results indicated that, under most conditions, ribosomes were degraded (in vivo) at similar rates in both the mesophile and the thermophile. In some studies, ribosome degradation rates were slightly faster for the thermophile than for the …

Purification And Characterization Of A Dna Polymerase From The Cyanobacterium Anacystis Nidulans R2, Hsiu-Jin Lin, Gordon C. Cannon, Sabine Heinhorst

Faculty Publications

A DNA polymerase has been highly purified from Anacystis nidulans R2. Electrophoretic analysis in sodium dodecyl sulfate-polyacrylamide gels revealed that the final fraction contains three bands of M_r 107,000, 93,000, and 51,000, respectively. Analysis of purified DNA polymerase activity in situ indicates that of the three polypeptides the M_r 107,000 species has the catalytic activities. The native molecular weight of the enzyme was estimated by glycerol gradient sedimentation to be 100,000. The enzyme has an absolute requirement for a divalent cation. Mg²⁺ can be replaced with Mn²⁺, but the DNA polymerase is less active. Potassium …

Kinetic-Energy Density Functional For A Special Shape-Invariant Potential Of A One-Dimensional Two-Level System , Jiushu Shao, John J. Stezowski

John J. Stezowski Publications

By introducing the concept of supersymmetry to quantum mechanics, several authors have shown that exactly soluble potentials, including all those well known, are easily constructed. Is the kinetic-energy density functional corresponding to these potentials a simple form? We show that the answer is no, even to the simplest one, the harmonic potential, if one builds the kinetic-energy density functional from the reduced density matrix.

Coupled Kinetic Analysis Of Cleavage Of Dna By Esperamicin And Calicheamicin, Hiroko Kishlkawa, Ying-Ping Jiang, Jerry Goodisman

Chemistry - All Scholarship

A coupled kinetic analysis of esperamicin, calicheamicin, and DNase I cleavage of covalently closed circular PM2 DNA has been carried out. Analysis of the optical density data derived from agarose gel electrophoresis experiments shows that esperamicin A,, like the hydrolytic enzyme DNase I, produces mainly single-strand breaks in DNA. These agents cause covalently closed circular form I DNA to be initially converted to nicked circular form I1 DNA. However, the ratio of the rate constant for this process (k,') to that associated with conversion of form I1 to linear form I11 DNA ( k i ) is not consistent with …

Part I: Oxidation Of Heavy Metal Sulfides In Relation To The Environment; Part Ii: Fundamental Theory & Experiments Concerning Gas Chromatography & Mass Spectrometry, Judith Morgan

Masters Theses & Specialist Projects

Oxidation of heavy metal sulfides is a thermodynamically spontaneous process. Because of this, metal sulfides in the presence of oxygen are not stable. Currently there are over 100 streams and rivers, within the U.S., contaminated with heavy metal mine drainage; therefore an approved method of restoration is necessary. Precipitation of heavy metals as sulfides using H₂S as a reductant has been favorably reviewed as a restorative technique to clean up mining areas. However, using this technique on the laboratory scale does not prove to be a viable answer and shows strong pH dependence.

In the past three years …

Spreadsheets And Their Relation To Reality (Presentation), Donald H. Stedman, Gary A. Bishop, James E. Peterson, Paul L. Guenther

Fuel Efficiency Automobile Test Publications

No abstract provided.

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Bis(1h+-Pyrazinium N4-Oxide) Dichromate, Gary L. Gard, Roger D. Willett, W. W. Paudler, R. M. Sheets, Mark R. Pressprich

Chemistry Faculty Publications and Presentations

2C₄H₅N₂O⁺.Cr₂O²₇⁻, Mᵣ=410∙2, monoclinic, P2₁, a=8∙(2), b=6∙132 (2), c=14∙493 (4) Å, β=94∙50 (2)°, V=708∙8 (3) ų, Z=2, Dₓ=1∙92 g cm⁻³, Mο Κα, λ=0∙71069 Å, μ=15∙5 cm⁻¹, F(000)=412, T=293 K, R=0∙0602 for 1980 unique observed reflections with F≥3σ(F). The structure consists of discrete dinegative dichromate anions hydrogen bonded to monopositive pyrazinium N-oxide cations (N―H∙∙∙O=2∙724, 2∙644 Å). A strong hydrogen bond to the bridging O atom in the Cr₂O²₇⁻ anion leads to significant lengthening of the bridging Cr―O bonds. A short C―H∙∙∙O interaction (3∙180 Å) is also observed.

Reductive Chemistry Of Dicyanoalkane Reactive Intermediates, Beshakeh Fonkeng

Masters Theses & Specialist Projects

Radical ions are reactive intermediates that are both radicals and ions (either a radical cation or a radical anion). The intrinsic properties of radical ions are not yet well -characterized. Such knowledge is mechanistically important to the organic chemist.

The specific question that motivates this research is as follows: is it possible to controllably express free radical processes in a radical ion independent of ionic chemistry (and vice versa) and, if so, what factors dictate which type of chemistry is expressed?

Our investigation focused on the chemistry of radical anions of dicyanoalkanes that are formed upon metal reduction. Factors influencing …

Argon-Photoion–Auger-Electron Coincidence Measurements Following K-Shell Excitation By Synchrotron Radiation, Jon C. Levin, C. Biedermann, N. Keller, L. Liljeby, C.-S. O, R. T. Short, Ivan A. Sellin, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Argon photoion spectra have been obtained for the first time in coincidence with K-LL and K-LM Auger electrons, as a function of photon energy. The simplified charge distributions which result exhibit a much more pronounced photon-energy dependence than do the more complicated noncoincident spectra. In the near-K-threshold region, Rydberg shakeoff of np levels, populated by resonant excitation of K electrons, occurs with significant probability, as do double-Auger processes and recapture of the K photoelectron through postcollision interaction.

Concomitant Ordering In First Row Transition Metal Fluorides, Ajay Shah

Electronic Theses and Dissertations

Type of Compounds Investigated

First row transition metal fluorides with a general formula, A_xM²⁺_xM’³⁺_1-xF₃, where A = alkali metal ion, M,M' = First row transition metal ions, and x = 0 - 1 ate reported to form, ReO₃, perovskite, GdFeO₃, tetragonal tungsten bronze (TTB), hexagonal tungsten bronze (HTB), and, modified pyrochlore type structures. Compounds of the type LiM^IIM^IIIF₆ have been reported to form rutile and trirutile type structures. These compounds display ionic, electronic, and magnetic ordering.

Formation of TTB Structure and …

Statics And Dynamics Of Organic Charge-Transfer Crystals: The Orientational Phase Transition In A-Tcnb, Karl-Heinz Brose, Tadeusz Luty, Craig J. Eckhardt

Craig J. Eckhardt Publications

Crystal potential energy calculations and lattice dynamical calculations are presented for the high-temperature and low-temperature phases of the charge-transfer complex crystal of anthracene with 1,2,4,5-tetracyanobenzene using the method of atom–atom potentials. For several different sets of the “exp-6'' potential parameters the crystal energy was minimized with respect to the lattice constants and orientations and positions of the molecules in the unit cell. These calculations show good agreement with the experimental values. The equilibrium crystal structures were used to calculate the lattice dynamics in the harmonic approximation for both crystal modifications. In the phonon dispersion curves lattice modes were discovered that …

32nd Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Program and registration information for the 32nd annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, July 29 - August 3, 1990.

Ua66/7/3 Coal & Fuel Characterization Laboratory: The First Ten Years, Wku Chemistry

WKU Administration Documents

Report of work completed in the first ten years of the Coal & Fuel Characterization Laboratory.

Stereocontrolled Iodolactonization Of Erythro And Threo Tertiary Amides, David Rotella, Xun Li

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

A series of α-mono and dialkyl-β-oxygenated (hydroxyl and alkyl ester) tertiary amides were subjected to iodolactonization and it was observed that with only 1 exception, (threo11b), all of the compounds cyclized with useful levels of stereoselection (at least 3:1). While the origin of this effect is obscure, these results suggest that in such amide substrates with at least one substituent larger than methyl α to the amide, iodolactonization is a viable strategy for the stereocontrolled preparation of highly substituted γ-butyrolactones.

A Potentiometric Gaseous Hydrogen Sensor, Anne Guillory

Chemistry & Biochemistry Theses & Dissertations

The development of a potentiometric gaseous hydrogen sensor using a 75% palladium - 25% silver alloy as a selectively hydrogen permeable electrode is described. The sensor showed some promise when used with a molten base electrolyte. Other electrolytes are investigated at ambient and higher temperatures. Various cell designs including a platinum/silver-silver chloride sensor with a gel electrolyte are discussed.

Mössbauer-Effect, Magnetic, And Neutron-Diffraction Study Of Nafep₂O₇, R. C. Mercader, L. Terminiello, Gary J. Long, D. G. Reichel, K. Dickhaus, R. Zysler, R. Sanchez, M. Tovar

Chemistry Faculty Research & Creative Works

Neutron-diffraction, magnetic-susceptibility, specific-heat, and Mössbauer-effect studies of NaFeP₂O₇ reveal that it is a normal Heisenberg isotropic three-dimensional antiferromagnetic material with a Néel temperature of 29.0 K. NaFeP₂O₇ has the monoclinic P2₁/c magnetic space group, which is the same as the nuclear crystallographic space group. The easy axis of magnetization lies in the monoclinic ac plane at an angle of 21.0° from the c axis. The specific-heat measurements reveal a λ-type anomaly at 28.7(2) K. A molecular-field model analysis indicates that the intrasublattice magnetic exchange coupling J_aa=J_bb=-0.37 cm-1, whereas …

Photoinduced Electron Transfer In Self-Associated Complexes Of Several Uroporphyrins And Cytochrome C, J. S. Zhou, E. S. V. Granada, Neocles B. Leontis, M. A. J. Rodgers

Chemistry Faculty Publications

Photoinduced electron transfer between cytochrome c and free base and metallouroporphyrin (Up, MUp) has been studied. Difference absorption spectrophotometry showed that the electrostatic interactions between Up and cytc(II1) result in their forming a self-associated 1:l complex in the ground state with a binding constant that depends upon the ionic strength. In the complex, the photoexcited uroporphyrin singlet state was quenched through a static interaction with the protein. Even under the most favorable quenching conditions, Le., when all porphyrin was complexed, residual fluorescence was noted. More significantly the excited singlet state of the complex was shown to undergo small, but significant, …

X-Ray Powder Diffraction, Scanning Electron Microscopy And Energy Dispersive Spectroscopy Studies Of Soil Containing Chromium Immobilized By Microwave Treatment, Nagui Ibrahim

Theses

The orientation of soil contaminants such as chromium is altered during microwave heating. The SEM and EDS were utilized in the study. The nature of the orientation is related to the heating time. This results in immobilizing the contaminant in leaching tests. The non-leachibility was related to the reactivity of the chromium salt with the soil hematite phase (Fe2O3) during the microwaving. This was proved By the X-ray diffraction analysis. The spectrums obtained from 30 and 60 minutes microwaved samples were identical in the crystal phases and were significantly different from the contaminated unheated sample.

Removal Of Heavy Metal Ions From Wastewater By Foam Flotation, Xue-Jun Tang

Theses

The foam flotation technique was used to remove Cr³⁺, Cr⁶⁺, Cu²⁺, Zn²⁺, Co²⁺, and Nz²⁺ from solution The simulated wastewater contained 20 - 50 ppm of each of these ions. Fe³⁺ is added into wastewater as coagulant to produce floc. These dissolved metal ions are adsorbed onto the floc and/or coprecipitate with them. The floc can be then removed from solution by foam flotation. Under optimal conditions, such as pH=6.3 - 7.4, Fe³⁺=160 ppm for hexavalent Chromium or 90 ppm for others and Lauryl Sulfate=90 ppm, …

Two-Dimensional Gel Electrophoretic Analysis Of Cellular Proteins From Escherichia Coli In The Presence Of Mutated And Homologous Genes For 4.5s Rna, Michael O'Loughlin

Senior Scholar Papers

4.5S RNA is a small. stable, required molecule in Escherichia coli whose precise function is not known. Previous evidence suggests an involvement with the ribosome during translation. In this study, four base insertion and four base deletion mutations were constructed in a plasmid borne copy of the 4.55 RN A gene. These copies and two homologous genes from Pseudomonas aeruginosa and Thermus thermophilus were transformed into an E. coli strain which then had its only wild-type 4.5S RNA gene inactivated. In order to assess the effect of the alternative gene copies. the patterns of proteins synthesized in the presence of …

Measuring Δh Using Dsc, Tga & Dta, Roland Hoffman

Masters Theses & Specialist Projects

The purpose of this study was to obtain greater accuracy in the measurement of the heat of reaction by combining data from various thermal analysis techniques. Conventional equations that calculate heat of reaction are limited because they do not take in to account mass change. Therefore, an enhanced equation was developed to integrate mass (weight) change to provide greater accuracy. The path chosen to implement this new equation employed simultaneous Thermogravimetric / Differential Thermal Analysis (TG/DTA) that could provide both ΔT and weight data simultaneously. Computer programs were written in C and Pascal languages to provide communication capabilities between computers …

A Prostaglandin Synthase Inhibition Assay With Detection By Elisa, Patricia Scott

Theses & Honors Papers

A simple, reliable method is described for the routine measurement of non-steroidal anti-inflammatory drugs (NSAIDs) as inhibitors of prostaglandin synthase. Appropriate concentrations of inhibitor are incubated with ram seminal vesical prostaglandin synthase, sodium arachidonate and reduced glutathione. Prostaglandin E₂ (PGE₂) production is then quantitated by and enzyme linked immunosorbant assay (ELISA), in which anti-PGE₂ antibody is utilized in a binding competition between test sample and adsorbed conjugate of PGE₂-BSA. The antibody which remains bound to the solid phase is quantitatively determined colorimetrically by incubation with horse radish peroxidase labeled goat anti-rabbit IgG followed by …

Polar-Liquid, Derivatized Cyclodextrin Stationary Phases For The Capillary Gas Chromatography Separation Of Enantiomers, Daniel W. Armstrong, Weiyong Li, Chau Dung Chang, Josef Pitha

Chemistry Faculty Research & Creative Works

A new class of hydrophilic, relatively polar liquid, cyclodextrin (CD) derivatives have been used as highly selective chiral stationary phases (CSPs) for capillary gas chromatography (GC). Several possible requirements for liquidity In CD derivatives are discussed. O-(S)-2-Hydroxypropyl derivatives of α-, β-, and γ-cyclodextrlns were synthesized, exclusively characterized, permethylated, and evaluated for enantloselectlvity. Seventy pairs of enantiomers were resolved. They represent a wide variety of structural types and classes of compounds including chlral alkyl amines, amino alcohols, epoxides, pyrans, furans, sugars, dlols, esters, ketones, bicyclic compounds, alcohols, and so on. Many of these compounds were not aromatic and cannot be resolved …

Thermodynamic Data From Drug-Dna Footprinting Experiments, James C. Dabrowiak, Jerry Goodisman, Koren Kissinger

Chemistry - All Scholarship

Sequence-dependent thermodynamic quantities for the antiviral agent netropsin and a related bis(N-methylimidazole) dipeptide, lexitropsin, have been determined by DNase I footprinting techniques. The primary data are autoradiographic spot intensities derived from 10 footprinting experiments carried out in the temperature range 0-45 OC. After exclusion effects due to overlapped drug sites on DNA and redistribution phenomena associated with the enzyme were accounted for, sequence-dependent binding constants for the two ligands were calculated. Our approach does not require an independent determination of the free drug concentration, which is calculated, with individual site binding constants, by using only footprinting data. The temperature dependence …

Photochemistry Of Nitrous Acid And Nitrite Ion, Christopher L. Exstrom '90

Honors Projects

Aqueous solutions of HONO (ranging from 0.010M to 0.057M) and NO2 (ranging from 0.025M to 0.035M) were each photolyzed with nm ultraviolet (UV) light. In the presence of benzene scavenger, DH radical intermediate was indicated by formation of p-nitrosophenol (PNP). Ultraviolet/visible (UV/vis) absorption spectra of photolyzed aqueous HONO/benzene solutions showed the presence of PNP by its characteristic absorption at 298 nm. UV/vis absorption spectra of photolyzed aqueous NO -benzene solutions showed no evidence of PNP formation. Other compounds such as scavengers were toluene, benzoic acid, and terephthalic acid. UV/vis spectra of photolyzed aqueous HOND/scavenger solutions showed an Int n e …

Kinetics Of The Metal-Exchange Reaction Between Ortho-Phospho-Dl -Serinenickelate(Ii) And Copper(Ii), Jeffrey M. Peterman

Masters Theses

No abstract provided.