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Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Thermal Characterization Of Carbon Monoxide Oxidation Catalysts Using Thermogravimetric Analysts And Differential Scanning Calorimetry, Rene A. Bartgis

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin (IV) oxide supports, with and without silica gel, as well as catalysts composed of gold on manganese oxide, have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A thermogravimetric method and a differential scanning calorimetric method have been developed for the thermal characterization of these catalysts. The mass loss data and the enthalpy changes determined as the catalysts lost water were then related to existing activity data for these catalysts. No relationship was found between the thermal data and the …

Remote Sensing Enhanced Motor Vehicle Emissions Control For Pollution Reduction In The Chicago Metropolitan Area: Siting And Issue Analysis, Carol E. Lyons, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Reactions Of Aqueous Chlorine With Valine In Model Solutions And In Wastewater, Erika Forrer Mccormick

Chemistry & Biochemistry Theses & Dissertations

Solutions of the amino acid valine were chlorinated to seven chlorine-to-nitrogen mole (Cl/N) ratios and analyzed by high performance liquid chromatography, gas chromatography/mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The chlorination products found were N-chlorovaline, isobutyraldehyde, isobutyronitrile, and N-chloroisobutyraldimine. Their product distribution depends on the level of chlorination and pH. The main products identified at the lower CI/N mole ratios were N-chlorovaline and isobutyraldehyde, whereas at the higher CI/N mole ratios isobutyronitrile and N-chloroisobutyraldimine were identified as the main products. The concentration and the chlorination products of valine in municipal wastewater were also determined. The chlorination products of …

Site-Specific Binding Constants For Actinomycin D On Dna Determined From Footprinting Studies, Jerry Goodisman, Robert Rehfuss, Brian Ward, James C. Dabrowiak

Chemistry - All Scholarship

We report site-specific binding constants for the intercalating anticancer drug actinomycin D (Act-D), binding to a 139-base-pair restriction fragment from pBR 322 DNA. The binding constants are derived from analysis of footprinting experiments, in which the radiolabeled 139-mer is cleaved using DNase I, the cleavage products undergo gel electrophoresis, and, from the gel autoradiogram, spot intensities, proportional to amounts of cleaved fragments, are measured. A bound drug prevents DNase I from cleaving at -7 bonds, leading to decreased amounts of corresponding fragments. With the radiolabel on the 3’ end of the noncoding strand (A-label), we measured relative amounts of 54 …

Structural Changes And Enhancements In Dnase I Footprinting Experiments?, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

In footprinting experiments, an increase in DNA cleavage with addition of ligand to a system may be due to a ligand-induced structural change. Ligand binding also enhances cleavage by displacing the cleavage agent from ligand-binding sites, thus increasing its concentration elsewhere. The theory and characteristics of this mass-action enhancement are given, and it is shown how it may be recognized. Results of DNase I footprinting of small oligomers, with actinomycin D as ligand, are analyzed to reveal which enhancements are due to mass action, and which can reasonably be ascribed to structural changes. Patterns in the footprinting plots from our …

Reply To "Comment On '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

For a harmonic potential, which is the special shape-invariant potential discussed in our paper [1], the relation between the ground state and the first-excited-state wave functions [Eq. (2)] should be . . .

Therefore, we have shown that one cannot find a closed form of the kinetic-energy density for the harmonic oscillator.

Low Pressure Chemical Vapor Deposition (Lpcvd) Of Silicon Carbide From Diethylsilane, Yi-Tong Shi

Theses

The depositions of amorphous and cubic-crystal SiC from a new chemical vapor deposition source, diethylsilane(DES), have been studied. Amorphous SiC thin films and crystalline cubic-SiC materials have been deposited on silicon wafers at temperature lower and higher than 850C, respectively. The activation energy and a reaction mechanism involving the production and subsequent desorption of diethylsilene has been suggested, which explains the observed deposition dependency with the temperature and reactor pressure. A model based on the polymerization of DES is offered and the deposition rate is found to be the result of a large number of simultaneously occuring deposition processes for …

Low-Temperature Crosslinking Of Polycyclopentadiene, Lawrence Peters

Theses

Cyclopentadiene was polymerized via a Diels-Alder mechanism at 174°C under an inert atmosphere. The polymer obtained after ll hrs of reaction had a low bulk viscosity of 8 cps and a viscosity-average molecular weight, Mv, of up to 3000. An unsaturated polyester was synthesized from maleic anhydride and ethylene glycol in the presence of chlorosulfonic acid at room temperature. The polyester had an intrinsic viscosity of 0.024 cps. At 60°C, polycyclopentadiene (PCPD), and the unsaturated polyester were reacted to yield a viscous liquid which was crosslinked at room temperature over 48 hours in the presence of styrene, triethyleneglycol dimethacrylate (TEGDMA), …

Surface Tension Of A Charged And Polarized System, Jerry Goodisman

Chemistry - All Scholarship

Usually, the formula for the surface tension of a planar charged and polarized interface is obtained from that for a system involving only short-range forces, y = - dz [p - px(z)] by replacing the tangential pressure p , by p , + E2/8u. Problems with this include (a) p, is no longer explicitly defined, (b) the electrostatic stress term E2/8 pi is not correct in general but only if polarization is proportional to density of polarizable species, (c) the derivation of the formula in terms of p and p, involves calculating the work to expand a volume containing the …

Liquid Phase Electrochemistry At Ultralow Temperatures, Royce W. Murray, Stanton Ching, John T. Mcdevitt, Stephen R. Peck

Chemistry Faculty Publications

Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with or as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. …

Expression Of Biologically Active Human Corticosteroid Binding Globulin By Insect Cells: Acquisition Of Function Requires Glycosylation And Transport, Jayasri Ghose-Dastidar, J. B. Alexander Ross, Reza Green

Chemistry and Biochemistry Faculty Publications

Human corticosteroid binding globulin (hCBG) is a 50- to 55-kDa serum glycoprotein that binds cortisol and progesterone with high affinity. To map the steroid-binding domain and to investigate the folding pathways of hCBG, we have established an expression system based on infection of insect cells with a recombinant baculovirus encoding hCBG. Infected Spodoptera frugiperda (Sf9) cells secrete immunoreactive hCBG at high levels (16-24 pmol per 10⁶ cells per 40 h), and the recombinant protein binds cortisol with an affinity and specificity equivalent to that of human serum-derived hCBG. Thus, this system has the potential to provide large amounts of …

Measurement Of The Ratio Of Double-To-Single Photoionization Of Helium At 2.8 Kev Using Synchrotron Radiation, Jon C. Levin, Dennis W. Lindle, N. Keller, R. D. Miller, Y. Azuma, N. Berrah Mansour, H. G. Berry, Ivan A. Sellin

Chemistry and Biochemistry Faculty Research

We report the first measurement of the ratio of double-to-single photoionization of helium well above the double-ionization threshold. Using a time-of-flight technique, we find He⁺⁺/He⁺=1.6±0.3% at hν=2.8 keV. This value lies between calculations by Amusia (2.3%) and by Samson, who predicts 1.2% by analogy with electron-impact ionization cross sections of singly charged ions. Good agreement is obtained with older shake calculations of Byron and Joachain, and of Åberg, who predict 1.7%.

Anisotropy Of Polarized X-Ray Emission From Molecules, S. H. Southworth, Dennis W. Lindle, R. Mayer, P. L. Cowan

Chemistry and Biochemistry Faculty Research

Strongly anisotropic, polarized Cl K-V x-ray emission from gas-phase CF₃Cl has been observed following resonant excitation with a linearly polarized x-ray beam. Distinctively different angular distributions are observed for x-ray emission involving molecular orbitals of different symmetries. A classical model of the x-ray absorption-emission process accurately describes the observed radiation patterns.

On-Road Remote Sensing Of Co Emissions In The Los Angeles Basin, Donald H. Stedman, Gary A. Bishop, James E. Peterson, Paul L. Guenther

Fuel Efficiency Automobile Test Publications

Final report to the California Air Resources Board under Contract No. A932-189.

The University of Denver remote sensor for on-road motor vehicle carbon monoxide emissions was used for eleven days in the Los Angeles Basin in December, 1989. The remote sensor has been incorporated into the 1990 Clean Air Act Amendments as "on-road emissions testing". The device measures the CO/CO₂ ratio for one-half second behind each vehicle, from which the exhaust %CO is calculated. Vehicles were measured in a mix of many driving modes and speeds ranging from deceleration coming up to a red traffic light through idling in …

Micellar Catalysis Of Hydrolysis Of Substituted Hydroxamic Acids With Perfluorooctanoic Acid, Zhongyuan He

Masters Theses

The work demonstrated the effects of differently located and substituted phenyl groups, as well as aliphatic groups in the hydroxamic acids, on micellar catalysis with perfluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution.

Kinetic rate constant-surfactant concentration profiles for the decano-, 2,5-dimethylphenylaceto-, 4-isopropylphenylaceto-, 4-phenylbutano-, and 6-phenyl-hexanohydroxamic acids were examined and analysis on the data obtained were reported.

The pseudo-phase ion exchange (PPIE) model has been satisfactorily applied to explain the observed micellar effects.

Further investigation into more appropriately substituted hydroxamic acids is suggested in order to obtain a more complete set of data and further evaluation.

33rd Rocky Mountain Conference On Applied Spectroscopy

Rocky Mountain Conference on Magnetic Resonance

Program and registration information for the 33rd annual meeting of the Rocky Mountain Conference on Applied Spectroscopy, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 28 - August 1, 1991.

A Diffuse Reflectance Infrared Fourier Transform Spectroscopic Study Of Platinum/Tin (Iv) Oxide Low-Temperature Carbon Monoxide Oxidation Catalysts, Donna Sue Duarte

Chemistry & Biochemistry Theses & Dissertations

Platinum-coated tin(IV) oxide catalysts have been developed for the recombination of carbon monoxide and oxygen at 55°C and 1 atmosphere of pressure in closed-cycle carbon dioxide lasers. A diffuse reflectance infrared fourier transform spectroscopic (DRIFTS) study of four of these catalysts during 5% carbon monoxide pretreatment at temperatures of 30°C, 100°c, 125°c, and 150°C has been performed. Evidence for the development of surface carbonate, bicarbonate, and formate species during pretreatment has been found. Dehydroxylation of the surface and loss of a partially charged hydrogen-bonded hydroxyl species have also been found to result from elevated temperature pretreatment. The four catalysts have …

Stable N-Chloraldimines And Other Chlorination Products Of Phenylalanine In Model Solutions And In A Wastewater, Barbara L. Conyers

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid phenylalanine were chlorinated to seven Cl/N mole ratios. The by-products were characterized using gas chromatography, high performance liquid chromatography, GC/MS, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. At the lower Cl/N ratios N-chlorophenylalanine and phenylacetaldehyde were identified as the main products while phenylacetonitrile and N-chlorophenylacetaldimine were the major products at Cl/N ratios of 2.0 and beyond. The concentration of phenylalanine in a municipal wastewater was determined. Using a radiotracer the chlorination products of phenylalanine in the wastewater at the 7 Cl/N ratios were identified as those seen in the model solutions. The distribution of …

Ua3/8/1 John Robinson Professorship Report, Wku Ogden College Of Science & Technology

WKU Administration Documents

Report by Dr. John Riley, John Robinson Professor of activities for 1990-1991 funded by Ogden Foundation.

Formation Of Pentosidine During Nonenzymatic Browning Of Proteins By Glucose, Daniel G. Dyer, James A. Blackledge, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

A fluorescent compound has been detected in proteins browned during Maillard reactions with glucose in vitro and shown to be identical to pentosidine, a pentose- derived fluorescent cross-link formed between arginine and lysine residues in collagen (Sell, D. R., and Monnier, V. M. (1989) J. Biol. Chem. 264, 21597- 2 1602). Pentosidine was the major fluorophore formed during nonenzymatic browning of ribonuclease and lysozyme by glucose, but accounted for <1% of nondisulfide cross-links in protein dimers formed during the reaction. Pentosidine was formed in greatest yields in reactions of pentoses with lysine and arginine in model systems but was also formed from glucose, fructose, ascorbate, Amadori compounds, 3-deoxyglucosone, and other sugars. Pentosidine was not formed from peroxidized polyunsaturated fatty acids or malondialdehyde. Its formation from carbohydrates was inhibited under nitrogen or anaerobic conditions and by aminoguanidine, an inhibitor of advanced glycation and browning reactions. Pentosidine was detected in human lens proteins, where its concentration increased gradually with age, but it did not exceed trace concentrations (55 Fmol/mol lysine), even in the 80-year-old lens. Although its precise carbohydrate source in vivo is uncertain and it is present in only trace concentrations in tissue proteins, pentosidine appears to be a useful biomarker for assessing cumulative damage to proteins by nonenzymatic browning reactions with carbohydrates.

Decrease In Skin Collagen Glycation With Improved Glycemic Control In Patients With Insulin-Dependent Diabetes Mellitus, Timothy J. Lyons, Karen E. Bailie, Daniel G. Dyer, John A. Dunn, John W. Baynes

Faculty Publications

Glycation, oxidation, and nonenzymatic browning of protein have all been implicated in the development of diabetic complications. The initial product of glycation of protein, fructoselysine (FL), undergoes further reactions, yielding a complex mixture of browning products, including the fluorescent lysine-arginine cross-link, pentosidine. Alternatively, FL may be cleaved oxidatively to form N(epsilon)-(carboxymethyl)lysine (CML), while glycated hydroxylysine, an amino-acid unique to collagen, may yield N(epsilon)-(carboxymethyl)hydroxylysine (CMhL). We have measured FL, pentosidine, fluorescence (excitation = 328 nm, emission = 378 nm), CML, and CMhL in insoluble skin collagen from 14 insulin-dependent diabetic patients before and after a 4-mo period of intensive therapy to …

Nonlinear Optical Properties Of Bacteriorhodopsin: Assignment Of The Third-Order Polarizability Based On Two-Photon Absorption Spectroscopy, Robert R. Birge, Mark Masthay, Jeffery A. Stuart, Jack R. Tallent, Chian-Fan Zhang

Chemistry Faculty Publications

The third-order (pi) -electron polarizability, (gamma) (pi), of bacteriorhodopsin in the 0.0 - 1.2 eV optical region is assigned based on an analysis of the experimental two-photon properties of the low-lying singlet state manifold. The following selected values of (gamma) (pi) (units of 10-36 esu) are observed: (gamma) (0;0,0,0) equals 2482 +/- 327; (gamma) (-3(omega) ;(omega) ,(omega) ,(omega) ) equals 2976 +/- 385 ((omega) equals 0.25 eV), 5867 +/- 704 ((omega) = 0.5 eV), 14863 +/- 1614 ((omega) = 0.66 eV), 15817 +/- 2314 ((omega) equals 1.0 eV), 10755 +/- 1733 ((omega) equals 1.17 eV). The third-order polarizability of this …

Reactivities Of Some Aromatic Compounds At Supercritical Water Conditions, Chun-Cheng Tsao

Masters Theses

The goals of this study are the removal of nitrogen from the extraction products of coal by Supercritical Water and the development of an understanding of the reactions leading to this removal. Six model compounds with structures similar to the intermediates of the coal liquefaction processes were studied. Benzylamine generated toluene through hydrogen abstraction after the C-N bond rupture. To a lesser extent, the oxidation of the benzylic carbon took place leading to benzene formation. Both reaction pathways occurred with equal probability for benzylidenebenzylamine, producing comparable yields of benzene and toluene. Benzaldehyde generated benzene through the oxidation/decarboxylation sequence. Benzyl alcohol …

Methods Development For Determination Of Trace Polar Volatile Organics In Environmental Samples, Qingchu Peng

Theses

The determination of trace levels of organic compounds in water samples is well developed for the less polar compounds, but the polar compounds are more difficult. The development of reliable and reproducible methods for such compounds as volatile alcohols and ketones is necessary if environmental monitoring is to be extended to these compounds.

The purge-and-trap method is frequently used for determination of volatiles in water samples. The method has problems when hydrophylic substances are being analyzed, since these are less easy to purge from the solution and more difficult to trap and desorb quantitatively. The high amount of water carried …

Preparation And Testing Of Novel Dental Adhesives Based On Bis- Gma/Tegdma Monomer System, Deyun Sun

Theses

In this study, polymerizable phosphonate adhesives synthesized from Diethylchloro-phosphate and 2-Hydroxyethylmethylacrylate and formulated with G-methacryloxy-propyltrimethoxy silane is used in Bis-GMA/TEGDMA monomer system. All the raw materials and finished products are characterized with infrared spectra, vapor pressure osmometry, viscosity and gel test. The bonding strength to tooth materials is determined by Instron machine. The work emphasizes applying polymeric organic phosphonate adhesive to Bis-GMA/TEGDMA monomer system and investigates the appropriate conditions for the crosslinking of Bis-GMA/TEGDMA monomer system. Average bonding strength of 744 psi to enamel and 600 to dentine are ob¬tained in comparision to 550 psi to enamel for phosphonate/silane/MMA/PMMA and …

Evidence For An Unusual Kinetic Phenomenon In The Metallation Of Porphyrins, F. González-Vílchez, R. A. Vilaplana, Robert F. Pasternack

Chemistry & Biochemistry Faculty Works

Reaction of copper(II) with water soluble porphyrins (H₂porph) in the presence of ethylenediamine shows an unusual and so far unreported kinetic phenomenon that can be explained in terms of supramolecular assembly formation apparently involving all solute species as confirmed via light scattering and conductivity measurements.

Evolved Gas Analysis Using Coupled Tg-Cg & Tg-Ftir, Keith Bradfield

Masters Theses & Specialist Projects

Thermal analysis methods have ben used for many years for material characterization. In recent years, thermal methods have been coupled to other methods of chemical analysis to obtain more complete material characterization. This study looks at thermal decomposition of polymer samples as well as coal samples in atmospheres of nitrogen and air. The thermal analysis instrument used was coupled to a Gas Chromatograph (GC) and a Fourier Transform Infrared Spectrometer (FTIR) so that the gaseous products evolved during thermal decomposition could be analyzed. The results obtained show that the coupled techniques of TG -GC and TG-FTIR can show pyrolysis and …

Structure Of 2,9-Dimethyl-1,10-Phenanthroline Hemihydrate, Doyle Britton, Larry C. Thompson, Richard C. Holz

Chemistry Faculty Research and Publications

C₁₄H₁₂N₂•½H₂O, M_r = 217•27, tetragonal I4₁/a, a = 14•258 (3), c = 22•286 (4) Å, V = 4531 (3) ų, Z = 16, D_x = 1•274 (1) g cm^-3, Mo Kα radiation λ = 0•71073 Å, µ = 0•74 cm^-1, F(000) = 1840, T = 297 K, R = 0•041 for 1196 unique observed reflections with I > 2σ(I). Pairs of dimethylphenanthroline molecules related by a twofold axis are bridged by water molecules lying on the twofold …

The Limitations Of Women In Science At Six Midwestern Colleges Due To The Adherence To Conceptions Of Gender Differences Between The Sexes In The Years Of 1880 Through 1940, Denise Mohney '91

Honors Projects, History

It is difficult for college students today to imagine life when the term "discrimination" had not yet been defined or conceived. Yet only a little more than a hundred years ago women were first entering the academic world alongside men. These were often middle class women whose primary interactions with men had been through courtship and marriage. It was questioned whether women's intellectual ability and physical stamina were strong enough to persevere through the college experience. Scientists and physicians, writing for the general public, cited evidence that besides physical distinctions between the sexes, there were also intellectual and emotional differences. …