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Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Archives Records

Newsletter created by and about the WKU Chemistry department.

Optimization Of The Tungstic Acid Denuder Technique For The Measurement Of Atmospheric Ammonia, Patricia Diane Roberts

Chemistry & Biochemistry Theses & Dissertations

Measurement of - atmospheric ammonia with the tungstic acid denuder technique is discussed. Characterization of denuder tubes for manual sampling in terms of, repeatability, reliability and the development of ammonia blank signals was determined. Field testing of the manual sampling apparatus was performed at ground test sites and in a biomass burn smoke plume. Ammonia emissions from biomass burning are discussed.

The Synthesis And Evaluation Of 5-Phenyloxazolidines As Potential Cardiovascular Drugs, Tammy C. Wang

Chemistry & Biochemistry Theses & Dissertations

Drugs such as adrenoceptor antagonists and certain centrally acting agents are known to lower blood pressure and thus serve as clinically useful antihypertensive agents. Norepinephrine 4, a natural ∝-adrenoceptor agonist, is the major agent associated with increased blood pressure in the periphery. Based on a careful structure-activity comparison, a series of substituted oxazolidines, 20, 21, 22 and 23, have been designed as possible antihypertensive candidates. Specifically, 22 and 23 have been synthesized to serve as potential norepinephrine antagonists.

Preliminary evaluation of these compounds indicated that they were not antihypertensive in nature. The more active compound, 23, …

Linkage Position In Oligosaccharides By Fast Atom Bombardment Ionization, Collision Activated Dissociation, Tandem Mass Spectrometry And Molecular Modeling, Roger A. Laine, Krishna M. Pamidimukkala, Alfred D. French, Randall W. Hall, Saeed A. Abbas, Rakesh K. Jain, Khushi L. Matta

Randall W. Hall

No abstract provided.

Gas-Phase And Computational Studies Of Pentacoordinate Silicon, Robert Damrauer, Larry W. Burggraf, Larry P. Davis, Mark S. Gordon

Mark S. Gordon

We have demonstrated that a wide variety of pentacoordinate silicon anions (siliconates) should be stable and can be prepared by combining the predictive powers of MNDO and ab initio computational methods and the flowing afterglow (FA) experimental technique. MNDO has been used to compute the anion affinities of 91 siliconates; all but five of these are predicted to be stable with respect to the loss of an anion. Twenty-four siliconates, most of them previously unreported, have been prepared and studied in the FA. The MNDO predictions were, in general, consistent with the experimental results and with trends previously reported by …

Transport Properties Of Ground State Oxygen Atoms, Paul M. Holland, Louis Biolsi Jr.

Chemistry Faculty Research & Creative Works

The transport properties of dilute monatomic gases depend on the two body interactions between like atoms. When two ground state oxygen atoms interact, they can follow any of 18 potential energy curves corresponding to O₂, all of which contribute to the transport properties of the ground state atoms. Transport collision integrals have been calculated for those interactions with an attractive minimum in the potential by accurately representingab initio quantum mechanical potential energy curves with the Hulburt-Hirschfelder potential. Repulsive ab initio potential energy curves have been accurately represented either with the exponential repulsive potential or with an exponential …

Surface-Enhanced Raman Study Of The Effect Of Electrode Potential And Solution Ph Upon The Interfacial Behavior Of 4-Pyridinecarboxaldehyde, Mark Anderson, Dennis Evans

Mark R. Anderson

Surface-enhanced Raman scattering (SERS) spectra were obtained at a silver electrode in aqueous solutions at potentials from -0.2 to -0.6 V vs SCE and pH 1-7. The forms of 4-pyridinecarboxaldehyde that are adsorbed parallel those present in solution. In particular, the fraction of adsorbed species that is protonated at -0.2 V varies with pH in a manner almost identical with the fraction that is protonated in bulk solution. The protonated compound exists almost completely in the hydrated form (gem-diol) in the interface just as it does in solution. At a given pH, the fraction protonated on the surface increases as …

The Effect Of Solvent Type On The Infrared Spectrum Of Carbon Monoxide Adsorbed On A Platinum Electrode, Stanley Pons, Mark Anderson, Daniel Blackwood

Mark R. Anderson

No abstract is currently available.

A Comprehensive Method To Characterize Mixed Conduction Electrolytes, Michael P. Setter, J. Bruce Wagner Jr.

Michael P. Setter

Determination of the electrical characteristics of an electrolyte is vitally important to the design of battery materials and sensors. A wide variety of parameters are available from both dc and ac measurements. Through the use of computer control and a custom multiplexor, we can perform dc polarization and ac impedance measurements on a sample, without replacing electrodes.

Theoretical Study Of Structure And Reactions Of Metalated Oximes And Oxime Ethers, Rainer Glaser, Andrew J. Streitwieser

Chemistry Faculty Research & Creative Works

The potential energy surfaces of acetaldoxime carbanion and its ion pairs formed with lithium and sodium cations ions have been explored with ab initio methods to model and study the regiochemistry of metalated oxime ethers. Planar structures of the carbanions produced by deprotonating acetaldoxime are minima on the potential energy surface. The syn-isomer is 2.6 Kcal/mole more stable than the anti. This difference is not a manifestation of cyclic conjugation but more likely is a result of electrostatic effects. Two chiral and almost isoenergetic minima have been located for the ion pairs formed by either of the isomeric carbanions with …

The Effect Of Preozonation On The Anaerobic Biodegradability Of Resistant Phenolic Compounds, Yi-Tin Wang, Pin-Chieh Pai, James L. Latchew

KWRRI Research Reports

Ozone pretreatment studies of four model phenolic compounds were conducted to evaluate the effects of ozonation on the anaerobic biodegradability and toxicity of these compounds. Two types of batch studies, the Biochemical Methane Potential (BMP) and the Anaerobic Toxicity Assay (ATA), were performed on samples ozonated upon phenol, o-cresol, 2,5-dichlorophenol, and 2,4-dinitrophenol.

Experimental results showed that toxic and refractory phenolic compounds were converted to methane gas by means of preozonation. In general, the biodegradable fraction of the oxidation products increased as the ozone dose was increased. However, ozonation to achieve at least 60% COD reduction was necessary to faciliate methane …

30th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 30th 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 31 - August 5, 1988.

Analysis Of Ferredoxin And Flavodoxin In Anabaena And Trichodesmium Using Fast Protein Liquid Chromatography, Karen Lorraine Jones

Dissertations and Theses

Iron is an essential nutrient for growth of photosynthetic microorganisms such as cyanobacteria and algae. Iron is required for proteins involved in the important processes of carbon and nitrogen assimilation. Low concentrations of iron in cultures or natural waters can lead to iron limitation which affects many aspects of algal metabolism. In natural waters, iron limitation can have effects on the patterns and rates of primary productivity.

The cellular content of certain proteins can be affected by media iron concentrations. Methods have been used that assay components of the cell as an indirect measure of iron nutritional status. For example, …

"The Infrared Spectra Of Carbon Monoxide Adsorbed On A Polycrystalline Platinum Electrode From Nonaqueous Solutions, Mark Anderson, Daniel Blackwood, Stanley Pons

Mark R. Anderson

No abstract is currently available.

Oxidative Degradation Of Glucose Adducts To Protein: Formation Of 3-(NE-Lysino)-Lactic Acid From Model Compounds And Glycated Proteins, Mahtab U. Ahmed, John A. Dunn, Michael D. Walla, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The chemistry of Maillard or browning reactions of glycated proteins is being studied in model systems in vitro in order to characterize potential reaction pathways and products in biological systems. In previous work with the Amadori rearrangement product N alpha-formyl-N epsilon-fructoselysine (fFL), an analog of glycated lysine residues in proteins, we showed that fFL was oxidatively cleaved between C-2 and C-3 of the carbohydrate chain to yield N epsilon-carboxymethyllysine (CML) and D-erythronic acid. We then detected CML in proteins glycated in vitro, as well as in human lens proteins and collagen in vivo (Ahmed, M. U., Thorpe, S. R., and …

Theoretical Studies Of Silabicyclobutanes And Silacyclobutenes, Cnsi4-Nh6 (N = 0-4), Jerry A. Boatz, Mark S. Gordon

Mark S. Gordon

The geometries of the silicon-substituted bicyclobutanes and cyclobutenes c.Si4-.H6 are predicted by using the 3-21G(d) basis set and SCF wave functions. Strain energies and heats of formation are predicted by using MP2/6-31G(d) energies in conjunction with the appropriate homodesmic reactions. Bent bond lengths are calculated by tracing the path of maximum electron density connecting two nuclei, with the 6-31 G(2d) basis set at the 3-21 G(d) structures.

Potentially Aromatic Metallocycles, Kim K. Baldridge, Mark S. Gordon

Mark S. Gordon

Ab initio molecular orbital theory is used to characterize a series of metal-substituted benzene and cyclopentadiene structures, with the heteroatom taken from the block in the periodic table bounded by groups IV-VI and periods 2-5. Structures are predicted with the 3-21G* basis set and SCF wave functions. The calculated bond lengths and bond angles are in general within 0.04 A and 2°, respectively, of the available experimental values. As a measure of the de localization stabilization, !::.£and t::..H0 values for the appropriate bond separation and superhomodesmic reactions are calculated with 3-21 G* Hartree-Fock energies for these compounds and some smaller …

Development Of An Analytical Method For The Detection Of Specific Cations Using Flow Injection Analysis, John G. Cummings

Honors Theses

A general approach for the development of an analytical method for the detection of specific cations using flow injection analysis has been investigated. In this approach, an ionophore (I), which is selective for the cation (M+) of interest, is noncovalently immobilized on a controlled pore glass (CPG) surface. A column of tygon tubing is then filled with the 1-CPG phase and placed in the cell compartment of a spectrofluorometer. When an aqueous mobile phase containing M+ and 8-anilino+naphthalene sulfonic acid (ANS) is pumped through the column, the M+ reversibly binds to the immobilized I, and the resulting complex then forms …

Interfacial Adhesion Of Fiberglass Reinforced Thermoplastic Composites, David Gascoyne

Honors Theses

The use of reinforced plastics is vast. A proper understanding of these materials and their properties is Important. The interface of a reinforced plastic influences many of the materials mechanical properties. This study of fiber reinforced composites was conducted to better understand the interfacial interactions between XENOY and E-Glass fibers. The research consisted of studying the effects of processing temperature, long term hydrolytic attack, and coupling agents, on the interface.

Conformations Of Dna Oligomers, Daniel Edward Vaughn

Honors Theses

This work examines the conformations of various ollgonucleotides as a function of two environmental conditions, neighboring base combinations and surrounding media. The conformations were determined by molecular mechanical energy refinement using the internal minimization function of a program written by Ken Miller. The first condition examined was the effect of various neighboring base combinations on the conformation of the interior base. Our results indicate that the NH2 a,,lino groups are the primary factors in determining differences in conformations of various base pairs sequences. One way in which the NH2 amino groups are able to affect the conformation of the molecule …

Spectral And Kinetic Studies Of The Interaction Of Cyanide And Detergents With Cobalt (Ii) Phthalocyanine In Dmso, Harry M. King Jr.

Masters Theses & Specialist Projects

Spectral and kinetic studies made on CoPc over a concentration range of 1.72 x 10^-6M – 1.00 x 10^-5M in DMSO are consistent with a monomer-dimer equilibrium at 303 K. The dimerization constant obtained at 303 K is 1.67 x 10⁴M^-1 and is two to three orders of magnitude smaller than those of several tetrasulfonated metallophthalocyanines in aqueous solution. The rate constants for the formation and dissociation of the CoPc dimer in DMSO at 303 K are 1.29 x 10²M^-1s^-1 and 7.20 x 10^-3s^-1, …

Gelled Emulsions With A High Water Content, C. Solans, J. G. Dominguez, J. L. Parra, J. Heuser, Stig Friberg

Chemistry Faculty Research & Creative Works

The structure of a gel containing 99% water, 0.5% of a nonionic surfactant and 0.5% of a hydrocarbon was investigated by analysis of its equilibrium phases and their state of dispersion by liquid helium freeze fracture electron microscopy. The gel consisted of aqueous droplets of micron size separated by a thin membrane of a lamellar liquid crystal and a W/O microemulsion with droplets varying between 200 and 1000 Å in diameter. © 1988 Steinkopff.

Synthesis Of Allylic Organotin Compounds For The Preparation Of Homoallylic Alcohols, Deborah R. Hermance

Honors Theses

The addition of an allylic organotin compound to an aldehyde in the presence of a Lewis acid affords the erythro homoallylic alcohol. Organotin compounds containing optically active constituents such as menthyl and myrtanyl have been prepared. The myrtanyl compound was used in the preparation of an allylic organotin, cinnamyl trimyrtanyl tin, for future reaction with benzaldehyde. The objective is to obtain both enantio- and diastereoselectivity in the addition reaction.

Synthesis Of Strained Bridgehead Lactams, Quansing Tu

Theses

While 1-Azabicyclo(3,3,1)nonan-2-one was originally thought to be difficult to synthesize, two different methods (DCC and di-n-butyltin oxide) will produce it with high yield. DCC is a strong reagent for absorbing water; the di-n-butyltin oxide method uses a Dean-Stark to remove water and is very useful. Bredt's rule influences the synthesis and stability of the N-bridgehead bicyclic lactams, this is apparent in the lactam series in the behavior of the (2,2,2) compounds and the (3,2,1) compound which we tried unsuccessfully to synthesize.

Detection And Determination Of N-Nitrosohexamethyleneimine In Benzenesulfonamide, N-[[(Hexahydro-1-H Azepin-1-Yl)Amino]-Carbonyl]-4 Methyl By Hptlc, Anulfo A. Valdez

Theses

A simple method, by High Performance Thin Layer Chromatography HPTLC), was developed for rapid determination of N-Nitrosohexamethyleneimine in Benzenesulfonamide, N-[((hexahydro-1 H Azepin-1-yl)amino]-Carbonyl]-4 methyl, (Tolazamide). Separation of N-Nitrosohe-xamethyleneimine from a Tolazamide solution in chloroform was obtained by precipitation of Tolazamide with n-heptane and by passing the resulting clear solution through a small silica column which was eluted with methanol.

Determination of the N-nitroso compound was achieved by ultraviolet irradiation of it on activated High Performance Silica Gel Plates. Detection was performed by spraying the plates with triethylamine and fluorescamine reagent giving a fluorescent product. Visual detection limits of 25 ppb were …

Theoretical Study Of The Decomposition Of Five-Coordinate Silicon Anions, Larry P. David, Larry W. Burggraf, Mark S. Gordon

Mark S. Gordon

We have performed a theoretical study of the decomposition of the five-coordinate silicon anions (siliconates) H3(CH3)SiOH- and (CH3) 4SiOH-. These ions can be formed from hydroxide ion attack on methylsilane or tetramethylsilane, respectively. Both MNDO and ab initio calculations show that removal of methane from the five-coordinate structure is likely, via a transfer of the proton from the OH group to an adjacent methyl substituent. This process we term anionic dissociative proton transfer, because the transition state is one in which the methyl group being removed is almost completely dissociated to methide ion before the proton transfer takes place. This …

A Cytochemical Study Of The Transcriptional And Translational Regulation Of Nuclear Transition Protein 1 (Tp1), A Major Chromosomal Protein Of Mammalian Spermatids, Mohammad A. Heidaran, Richard M. Showman, Wilson Stephen Kistler

Faculty Publications

Immunocytochemical localization and in situ hybridization techniques were used to investigate the presence of spermatid nuclear transition protein 1 (TP1) and its mRNA during the various stages of spermatogenesis in the rat. A specific antiserum to TP1 was raised in a rabbit and used to show that TP1 is immunologically crossreactive among many mammals including humans. During spermatogenesis the protein appears in spermatids as they progress from step 12 to step 13, a period in which nuclear condensation is underway. The protein is lost during step 15. An asymmetric RNA probe generated from a TP1 cDNA clone identified TP1 mRNA …

Synthetic Studies Toward Key Portions Of The Didemnins, Ok-Soon Kim

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Three different synthetic approaches toward N-[(2SR, 4S) - 4-hydroxy-2,5-dimethyl-3-oxohexanoyl]-Lleucine methyl esters were carried out by use of i) aldol condensation and amination ii) Claisen condensation and soft acid coupling reaction iii) methylation of Hia-Leu derivative in relatively high yields. (4S)-3-[(2SR, 4S)-2,5-Dimethyl-1,3-dioxo-4-(methoxyethoxy-methyloxy)hexyl]-4-(1-methyletheyl-2-oxazolidinone was prepared by the reaction of aldol condensation of lithium enolate of Evans' chiral auxilary in 80:20 diastereomeric ratio. A new method for the synthesis of (4S)-4-(t-butoxycarbonyl)amino-5-methyl-3-oxoheptanoic acid ethyl ester (Statone) was developed by the reaction of Boc-leucine with Meldrum's acid, followed by transesterification and decarboxylation in modest yield. Other a-amino acids also were applied to this methodology in …

1-Acyldihydropyridones As Synthetic Intermediates, Michael Andrew Foley

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The most efficient and stereoselective total synthesis of (+/-)- lausbine II to date has been achieved. The key steps in this are the copper-mediated conjugate addition reaction of the Grignard reagent of 1-bromo-4-chlorobutane to a dihydropyridone and a stereoselective reduction of a quinolizidinone.

Methodology has been developed for the convenient synthesis of 1-acyl-2-substituted-1,2,5,6-tetrahydropyridines. This was accomplished by adding novel alkylzinc iodides to the 1-acyliminium ion derived from N-phenoxycarbonyl-4-methoxy-1,2,3,4-tetrahydropyridine.

Interactions Of Vanadium Compounds With Reducing Equivalents: Evidence Of Free Radical Involvement And Possible Mechanisms Of Toxicity, Randal J. Keller

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Vanadium compounds have been reported to cause numerous toxicological effects including NAD(P)H oxidation and lipid peroxidation. The purpose of this thesis is to determine the active form of vanadium in causing these effects, and to determine any possible free radical involvement in these processes. Vanadium-stimulated oxidation of NADH was studied spectrophotometrically and by electron spin resonance spectroscopy. In 25 mM sodium phosphate buffer at pH 7. 4, vanadyl, (V(IV)), is slightly more effective in stimulating NADH oxidation than was vanadate (V(V)). Addition of a superoxide generating system, xanthine/xanthine oxidase, results in a marked increase in NADH oxidation by vanadyl, and …