Physical Sciences and Mathematics Commons^™

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 …

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 …

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 …

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.

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.

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, …

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 …

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 …

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.

Structure-Activity Relationships Of Retinoids In Developmental Toxicology, W. Brian Howard

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The teratogenic potency of retinoid analogs was determined in Syrian hamsters and compared to the teratogenic potency of all-trans-retinoic acid (all-trans-RA, ED₅₀ = 10.5 mg/kg). A total of 15 analogs having variations in the cyclohexene ring were evaluated following various amounts of single oral doses on day 8 of gestation. Retinoids containing a five- or six-membered ring were as teratogenic as all-trans-RA, provided they had sufficient lipophilic substituents on the ring. The same pattern emerged for retinoids that had six-membered aromatic ring substitution for the natural cyclohexene ring of vitamin A. Incorporation of a supplementary …

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 …

Enantioselective Synthesis Of (-)-Retigeranic Acid, Teresa L. Bryant

Theses & Honors Papers

A new enantioselective convergant approach to Retigeranic acid (1) using (2+3} cyclopentene annulation methodology was used. A vinyl cyclopropane (8) intermediate was formed from the enone (9) and the bromoester (10). This product (8) was then pyrolized to yield the triquinane ring system (7). The pyrolysis product was reduced and saponified to give one enatiomer of Retigeranic acid (1) in good yield.

Translational-Rotational Modes In Noncentrosymmetric Lattices: A Lattice-Dynamical Interpretation Of The Phenanthrene Phase Transition, R. Kulver, Craig J. Eckhardt

Craig J. Eckhardt Publications

A lattice-dynamical study has been used to elucidate the mechanism of the phase transition in phenanthrene. The calculation is consistent with the known lattice energy and crystal structure. Combination of experimental results with the calculated phonon dispersion curves and eigenmode symmetries yields a dynamic mechanism for the transition based on increasing density of higher-frequency modes upon approach to the transition temperature to the high-temperature phase. This motion, which may be associated with motion of hydrogen atoms in the molecule, confers a more three-dimensional character to the interactions and correlates well with the observed change in heat capacity.

Synthesis And Study Of Novel Quinoxaline Di-N-Oxide And 3-Acyl-2-Methylquinoxaline Di-N-Oxides, Cyprian Okwara Ogbu

Masters Theses

This research project consists of two parts. The first involved the synthesis of a novel quininoxaline di-N-oxide via benzofuroxan. The second part was the use of this compound as a synthetic precursor.

It was assumed that 3,4-dimethylaniline would be successfully converted to 5,6-dimethybenzofurazan 1-oxide (5,6-dimethybenzofuroxan) through a sequence of reaction steps. Fortunately, this assumption was correct as the desired compound was produced. This compound was utilized in synthesizing the novel 3-acetyl-2,6,7-trimethylquinoxaline 1,4-dioxide. From the structure of this adduct, it is believed that it will take part in condensation reactions associated with methyl ketones without disrupting the quinoxaline di-N-oxide framework, and …

Synthesis And Reactions Of A-Diketones And Preparation Of Some New Benzimidazoles, Mohamad Reza Agharahimi

Masters Theses

This report will discuss the synthesis of 2,5-dl-(p-chlorophenyl)-3,4-dioxoadiponitrile and its reactions. This compound exists in the form of 4,4'- dichloropulvinic nitrile which is a precursor to 4,4'-dichk>rovulpinic acid. These compounds have been shown to have antiinflammatory activity in rats.

The benzimidazole and pyridazine derivatives of 4,4'-dichioropulvinic nitrile and the benzimidazole derivative of 4,4'-dichk>rovuipinic acid are another group of compounds that are also believed to have useful biological activities. The Pinner synthesis of imidates is used to make the intermediate to the benzimidazole derivative of 4,4'-dichloropulvinic nitrile.

This report will include the methodology of the reactions and …

A Synthetic Approach To Novel Heterocyclic Herbicides, Paul Antony Pathadan

Masters Theses

The purpose of this research study was to prepare novel heterocyclic herbicides. The first phase of the project was to synthesize 1-(nitromethyl)-4-phthalazone.

In the second phase 1 - (nitromethyl)-4-phthalazone was treated with 1,3-propane-dithio-di-p-toluene sulfonate in presence of sodium hydride to get the target compound 4-(1'-nitro-l,3-dithiane)phthalazone.

It is believed that this compound might block the electron transport system of aerobic cells¹ . So further investigation of this compound may lead to novel herbicides.

Use Of 52Cr For The Quantitative Determination Of Red Cell Volume, Claude Michael Hanbury

Chemistry & Biochemistry Theses & Dissertations

Chromium-52 has recently been suggested for use as a new agent to label red cells for the in vivo quantitation of red cell volume (1). In this paper, the development and validation of a routine ⁵²cr labeling procedure is described.

The accuracy, precision, and detection limits of chromium analysis by Zeeman effect atomic absorption spectroscopy was evaluated in the concentration range of 1 - 10 ug Cr/L.

Red cell chromium uptake was evaluated as a function of time, temperature, and concentration. Red cells labeled with a 2.5 mg/L chromium solution for 30 minutes at room temperature exhibited optimal label …

Reactions Of Aqueous Chlorine In The Gastric Fluid Of The Rat, Michael Gary Nickelsen

Chemistry & Biochemistry Theses & Dissertations

Gastric fluid was recovered from Sprague-Dawley rats that had been fasted for 24 hr or 48 hr and administered 4 mL deionized water. The protein, carbohydrate and chloride ion content of the gastric fluid was determined.

When gastric fluid is chlorinated with radiolabeled chlorine to concentrations between 323 and 375 mg/L, analyzed by high performance chromatography followed by liquid scintillation counting, as much as 59% of the radiolabeled chlorine was associated with organic components of the gastric fluid.

Model studies with the aromatic amino acids and the protein pepsin showed the formation of chlorinated analogs. Two chlorinated amino acid derivatives …

Low Pressure Gas Flow Analysis Through An Effusive Inlet Using Mass Spectrometry, David Robert Brown

Chemistry & Biochemistry Theses & Dissertations

A mass spectrometric method for analyzing flow past and through an effusive inlet designed for use on the tethered satellite and other entering vehicles is discussed. Source stream concentrations of species in a gaseous mixture are determined using a calibration of measured mass spectral intensities versus source stream pressure for standard gas mixtures and pure gases. Concentrations are shown to be accurate within experimental error. Theoretical explanations for observed mass discrimination effects as they relate to the various flow situations in the effusive inlet and the experimental apparatus are discussed.