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The Reactions Of N-Phenylaminoiminomethanesulfonic Acid (Paimso) With Meldrum's Acid, Milana-Minja Maletic '91

Honors Projects

No abstract provided.

Molecular-Orbital Studies Via Satellite-Free X-Ray Fluorescence: Cl-K Absorption And K–Valence-Level Emission Spectra Of Chlorofluoromethanes, Rupert C. Perera, P. L. Cowan, Dennis W. Lindle, R. E. Lavilla, T. Jach, R. D. Deslattes

Chemistry and Biochemistry Faculty Research

X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting "satellite-free" x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These …

Polarized X-Ray-Emission Studies Of Methyl Chloride And The Chlorofluoromethanes, Dennis W. Lindle, P. L. Cowan, T. Jach, R. E. Lavilla, R. D. Deslattes, Rupert C. Perera

Chemistry and Biochemistry Faculty Research

A new technique sensitive to molecular orientation and geometry, and based on measuring the polarization of x-ray emission, has been applied to the Cl-containing molecules methyl chloride (CH₃Cl) and the chlorofluoromethanes (CF₃Cl, CF₂Cl₂, and CFCl₃) in the gas phase. Upon selective excitation using monochromatic synchrotron radiation in the Cl K-edge (Cl 1s) near-threshold region, polarization-selective x-ray emission studies reveal highly polarized molecular valence x-ray fluorescence for all four molecules. The degree and the orientation of the polarized emission are observed to be sensitive to the incident excitation energy near …

Fkb1 Encodes A Nonessential Fk 506-Binding Protein In Saccharomyces Cerevisiae And Contains Regions Suggesting Homology To The Cyclophilins, Gregory Wiederrecht, Leonardo Brizuela, Keith Elliston, Nolan H. Sigal, John Siekierka

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

FK 506, a powerful immunosuppressant that blocks allograft rejection by preventing T-cell activation, binds to an 11-kDa protein called the FK 506-binding protein (FKBP). Like cyclophilin, a cytosolic protein that binds another immunosuppressant, cyclosporin A, FKBP possesses peptidylprolyl cis-trans isomerase activity. We have isolated a genomic clone encoding the yeast FKBP (FKB1). The gene encodes a protein of 114 amino acids having a calculated M(r) of 12,158. Disruption of the gene shows that FKB1 is not essential for growth. A search of translated nucleic acid data bases revealed bacterial FKBP homologs in Neisseria meningiditis and Pseudomonas aeruginosa. Comparison of the …

Evaluation Of D-Amino Acid Levels In Human Urine And In Commercial L-Amino Acid Samples, Daniel W. Armstrong, J. D. Duncan, S. C. Lee

Chemistry Faculty Research & Creative Works

Detectable levels of four free D-amino acids (phenylalanine, tyrosine, tryptophan and leucine) were found in human urine. This was accomplished using a liquid chromatographic coupled column (i.e., achiral-chiral) method that was developed for the rapid and sensitive analysis of these compounds. The technique was tested on a series of commercial L-amino acids. Care was taken to minimize racemization. Trace to percent levels of contaminating D-enantiomers were found in all commercial samples. In urine the D-amino acids ranged from several hundredths of a percent up to percent levels of the corresponding excreted natural L-amino acids. There were no apparent correlations between …

Use Of Affinity Chromatography In Developing Acridinium Ester-Labeled Antibodies For An Immunometric Assay Of Parathyrin, David S. Hage, Bob Taylor, Pat Schryver, Pai C. Kao

David Hage Publications

In developing an immunometric assay of intact parathyrin (parathyroid hormone, PTH), we found that affinity chromatography is a useful tool in purifying and optimizing the labeling conditions for acridinium ester-labeled antibodies. ... In summary, affinity chromatography was found to be useful in the purification of acridinium ester-labeled antibodies, particularly for removing denatured antibodies from the prepared label and for monitoring the amount of active labeled antibodies produced.

In Vitro Assembly Of Apophytochrome And Apophytochrome Deletion Mutants Expressed In Yeast With Phycocyanobilin, Lily Deforce, Ken-Ichi Tomizawa, Naoko Ito, Dave Farrens, Pill-Soon Song, Masaki Furuya

Department of Chemistry: Faculty Publications

Recombinant pea type I phytochrome apoprotein expressed in yeast is shown to assemble in vitro with phycocyanobilin to produce a photoreversible phytochromelike adduct. As an initial investigation of the amino acid sequence requirements for chromophore incorporation, three phyA gene product deletion mutants were produced in yeast. Truncation of the N-terminal tail to residue 46 demonstrates that this region is not critical to bilin attachment, but a deletion mutant lacking 222 amino acids from the N terminus failed to yield holophytochrome in vitro, under the same conditions. A mutant comprising a deletion of the C terminus to residue 548 …

Ab Initio Study Of Intermolecular Potential Of H2o Trimer, G. Chalasinski, M. M. Szczesniak, P. Cieplak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Nonadditive contribution to the interaction energy in water trimer is analyzed in terms of Heitler–London exchange, SCF deformation, induction and dispersion nonadditivities. Nonadditivity originates mainly from the SCF deformation effect which is due to electric polarization. However, polarization does not serve as a universal mechanism for nonadditivity in water. In the double‐donor configuration, for example, the Heitler–London exchange contribution is the most important and polarization yields the wrong sign. Correlation effects do not contribute significantly to the nonadditivity. A detailed analysis of the pair potential is also provided. The present two‐body potential and its components are compared to the existing …

Is Cyclophilin Involved In The Immunosuppressive And Nephrotoxic Mechanism Of Action Of Cyclosporin A?, Nolan H. Sigal, Francis J. Dumont, Philippe L. Durette, John Siekierka, Laurence B. Peterson, Daniel H. Rich, Brian E. Dunlap, Mary Jo Staruch, Michael R. Melino, Samuel L. Koprak, Dorsey Williams, Bruce E. Witzel, Judith M. Pisano

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

In this report we have approached two questions relating to the mechanism of action of cyclosporin A (CsA). First, we address whether the major cytosolic protein for CsA, cyclophilin, is directly involved in mediating the immunosuppressive activity of this drug, and, in particular, whether inhibition of this protein's peptidyl-prolyl cis-trans isomerase (PPIase) activity results in inhibition of murine T cell activation. Second, we ask whether the nephrotoxicity observed with CsA is related to inhibition of PPIase-dependent pathways in cells other than lymphocytes. Using a series of 61 cyclosporin analogues, we generally found a good correlation between cyclophilin binding and immunosuppressive …

Ab Initio Study Of The Intermolecular Potential Of Ar–H2o, G. Chalasinski, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The combination of supermolecular Møller–Plesset treatment with the perturbation theory of intermolecular forces is applied in the analysis of the potential‐energy surface of Ar–H₂O. The surface is very isotropic with the lowest barrier for rotation of ∼35 cm⁻¹ above the absolute minimum. The lower bound for D_e is found to be 108 cm⁻¹ and the complex reveals a very floppy structure, with Ar moving freely from the H‐bridged structure to the coplanar and almost perpendicular arrangement of the C₂ –water axis and the Ar–O axis, ‘‘T‐shaped’’ structure. This motion is almost isoenergetic (energy change …

Organic Geochemistry And Petrography Of Spanish Oil Shales, Michael A. Kruge, Isabel Suarez-Ruiz

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Four of the principal oil shale units of Spain were examined by organic geochemical and petrographic methods. The samples included three lacustrine shales (Carboniferous from Puertollano, Cretaceous from Llames and Miocene from Rubielos de Mora) and one marine shale (Lower Jurassic from Punta del Cuerno ). The petrographic observations show a dominance of liptodetrinite associated with bitumen-stained mineral matter and alginite, as well as a paucity of structured terrestrial organic matter. Geochemical work shows that the soluble organic matter is a mixture of terrestrially derived and aquatic, with the lacustrine samples having the strongest land plant signatures. Low values of …

Spatial And Temporal Distribution Of Hydrogen Peroxide In The Equatorial Pacific Ocean, Renee Blanchard

Honors Theses

The concentration of hydrogen peroxide in the Equatorial Pacific was determined fluorometrically using the horseradish peroxidase catalyzed dimerization of (p-hydroxyphenyl)acetic acid. Vertical profiles were obtained between 9 ON and 3 oS on a longitudinal transect along 140 oW during June and July of 1990 on the RN Wecoma. Peroxide concentrations ranged from 25-80 nmol/L at the surface and decreased to the detection limit of 1 nmol/L at a depth of about 200 meters. Diel variations of hydrogen peroxide in the surface waters were observed over the period of 8 days. The variation in surface concentration may be attributed to the …

Aspects Of Sporinite Chemistry, Michael A. Kruge, John C. Crelling, Edwin J. Hippo, Stephen R. Palmer

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

With the recent advent of the ability to separate coal into maceral concentrates of high purity, the individual constituents of coal can now be analyzed separately, without their mutual interference, giving a much better understanding of the macromolecular structure of coal. The sporinites from two Pennsylvanian age coal samples (Illinois Basin, U.S.A.) were studied, one from a vitrinite-rich high-volatile bituminous coal, the other from a liptinite-rich high-volatile bituminous coal of slightly higher rank. Sporinites were isolated from each coal by density gradient centrifugation. The sporinite of the vitrinite-rich coal was compared chemically and petrographically with the parent coal and with …

Drop-Box Technique For Quantitative Sampling Of Macrofauna And Aquatic Plants At Restored And Natural Wetlands, J. Douglas Oliver, Andrew J. Leslie, William M. Bartodziej

Faculty Publications and Presentations

No abstract provided.

Status Of Aluminum As A Risk Factor For Dialysis Encephalopathy And Alzheimer's Disease, P. B. Gorelick, D. (Daniel) B. Hier, C. Mangone, S. Robbins, A. Plioplys, S. Kathpalia

Chemistry Faculty Research & Creative Works

No abstract provided.

Direct Determination Of Molecular-Orbital Symmetry Of H2s Using Polarized X-Ray Emission, R. Mayer, Dennis W. Lindle, S. H. Southworth, P. L. Cowan

Chemistry and Biochemistry Faculty Research

X-ray emission from the molecule H₂S is strongly polarized following excitation of a sulfur K-shell electron to an unoccupied subthreshold molecular orbital with a polarized x-ray beam. Changes in the polarization of the emission spectrum are observed as the incident beam's energy is swept across the subthreshold absorption resonance. The previously unresolved absorption resonance is shown experimentally to be primarily associated with a molecular orbital of b₂ symmetry, but with a high-excitation-energy component due to an orbital with a₁ symmetry. Satellite emission intensity is shown to depend on the primary photon energy and is therefore associated …

Activator-Inhibitor Control Of Tissue Growth, John A. Adam

Mathematics & Statistics Faculty Publications

This note develops a simple model for the competition between activator and inhibitor control mechanisms in one-dimensional tissue growth. The pedagogic usefulness of such a model is that it is easily accessible to undergraduate applied mathematicians and is suggestive of behavior known to occur in more realistic biological systems (e.g., some types of cancer). The limitations of the model are obvious and can provide a basis for discussion of the applicability of complementary levels of description in mathematical modeling.

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 …

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, …

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 …

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 …

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

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.

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.

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, …

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 …

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 …