Digital Commons Network^™

Inulin-125I-Tyramine, An Improved Residualizing Label For Studies On Sites Of Catabolism Of Circulating Proteins, Janet L. Maxwell, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Residualizing labels for protein, such as dilactitol-125I-tyramine (125I-DLT) and cellobiitol-125I-tyramine, have been used to identify the tissue and cellular sites of catabolism of long-lived plasma proteins, such as albumin, immunoglobulins, and lipoproteins. The radioactive degradation products formed from labeled proteins are relatively large, hydrophilic, resistant to lysosomal hydrolases, and accumulate in lysosomes in the cells involved in degradation of the carrier protein. However, the gradual loss of the catabolites from cells (t1/2 approximately 2 days) has limited the usefulness of residualizing labels in studies on longer lived proteins. We describe here a higher molecular weight (Mr approximately 5000), more efficient …

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Kinetics And Mechanisms Of The Aminolysis Of N-Hydroxysuccinimide Esters In Aqueous Buffers, Gary W. Cline, Samir B. Hanna

Chemistry Faculty Research & Creative Works

Rate constants for the aminolysis of the N-hydroxysuccinimide (NHS) ester of ρ-methoxybenzoic acid, in aqueous buffer systems (20% dioxane), have been determined under pseudo-first-order conditions. For the amines studied (pK_a = 7.60-11.1), the data fit the rate expression k_obsd - K_OH-⨯ [OH-] = k₁[amine]_free. This rate equation is in contrast to the two-term rate equation (k_obsd = k₁[amine] + k₂[amine]²) obtained for this reaction in anhydrous dioxane (Cline, G. W.; Hanna, S. B. J. Am. Chem. Soc. 1987,109, 3087) and is suggestive of a disproportionate …

Enantiomeric Resolution And Chiral Recognition Of Racemic Nicotine And Nicotine Analogues By Β-Cyclodextrin Complexation: Structure-Enantiomeric Resolution Relationships In Host-Guest Interactions, Jeffrey I. Seeman, Henry V. Secor, Daniel W. Armstrong, Karen D. Timmons, Timothy J. Ward

Chemistry Faculty Research & Creative Works

High-performance liquid chromatography using β-cyclodextrin bonded phases was examined for the enantiomeric separation of racemic nicotine and 19 racemic nicotine analogues. Ten pairs of enantiomers were separated by this technique. This represents the first reported facile and direct separation of these racemates. Effects of pH, mobile phase composition, and structural features of the substrates (i.e., position and size of substituents, presence of pyrrolidine ring or hydrogen bonding functionalities, basicity) on the enantioselectivity are examined. Various structural aspects of the compounds were related to retention to the cyclodextrln-modlfied support and to the enantiomeric separations observed. Implications of this work to host-guest …

Use Of Secondary Equilibria For The Separation Of Small Solutes By Field-Flow Fractionation, Alain Berthod, Daniel W. Armstrong, J. Calvin Giddings, Marcus N. Myers

Chemistry Faculty Research & Creative Works

The dynamic range and selectivity of field-flow fractionation (FFF) can be Increased by using secondary chemical equilibria (SCE). SCE are established by adding a macromolecular additive or aggregate, which strongly Interacts with the field, to the carrier solution. In this study an oil-ln-water (O/W) microemulsion was used as the carrier solution in a sedimentation FFF apparatus. The microemulsion droplets (referred to as the "support") interact with the field and are retained relative to the bulk water. Small solutes that partition or bind to the microemulsion droplets are also retained relative to solutes that do not Interact with the support. In …

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, …

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 …

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, …

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 …

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 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 …

Fuel Efficiency Automobile Testing (F.E.A.T.), Donald H. Stedman, Gary A. Bishop, James A. Armstrong, Jackie Maddox

Fuel Efficiency Automobile Test Publications

Report to the Colorado Office of Energy Conservation

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 …

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.

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 …

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 …

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.

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.

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 …

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 …