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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 …

Chalcogen Elements In Snow: Relation To Emission Source, Kuen Y. Chlou, Oliver Manuel

Chemistry Faculty Research & Creative Works

We have measured the concentrations of S, Se, and Te in samples of 1986 snow and compared our results with those of earlier measurements. We were unable to find any earlier reports on Te in snow, but values of the Se/S concentration ratio in 1986 are about a factor of 6 lower than that in snow and glacial ice of 800 B.C. Measurements on intermediate samples demonstrate that most of the decline in the Se/S ratio occurred during the past 200 years, i.e., since the start of the Industrial Revolution. This temporal change in values of the Se/S ratio probably …

A Theoretical Investigation Of Several Low-Lying States Of Trans, Trans-1,3,5-Hexatriene, Robert J. Cave, Ernest R. Davidson

All HMC Faculty Publications and Research

Results from ab initio calculations concerning several low-lying electronic states of trans,trans-1,3,5-hexatriene are presented and compared with experimental and previous theoretical results. The lowest excited singlet state is predicted to be the ¹B_u state, having essentially valencelike π → π* character. The nominally doubly excited 2¹A_g state is found to lie approximately 0.6-0.9 eV above the 1¹B_u state. Results are also presented for several Rydberg states. The implications of the present results for current parametrizations of semiempirical π molecular orbital schemes are discussed.

The Spectroscopy And Molecular Dynamics Of The High Frequency Ν1 6 Intermolecular Vibrations In Hcn‐‐‐Hf And Dcn‐‐‐Df, B. A. Wofford, M. W. Jackson, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Gas phase rovibrational analysis of the high frequency intermolecular hydrogen bonded bending overtone 2ν⁰ ₆ [ν₀=1132.4783(2) cm^{− 1}] in HCN‐‐‐HF and its corresponding perdeuterated fundamental ν¹ ₆ [ν₀=409.1660(2) cm^{− 1}] are reported. Evaluated rovibrational parameters provide the basis for quantitative modeling of the molecular dynamics associated with this vibration. A quantum mechanical calculation permits determination of the quadratic and quartic force constants K _{6 6}=537(17) and K _{6 6 6 6}=4.98(12) cm^{− 1} which in turn are used to estimate the pertinent cubic band stretching interaction constants …

Erratum: Determination Of Dissociation Energies And Thermal Functions Of Hydrogen Bond Formation Using High Resolution Ftir Spectroscopy [J. Chem. Phys. 8 7, 5674 (1987)], B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Erratum

A Study Of Surface Dynamics Of Polymers. Ii. Investigation By Plasma Surface Implantation Of Fluorine–Containing Moieties, T. Yasuda, T. Okuno, K. Yoshida, H. Yasuda

Chemistry Faculty Research & Creative Works

Macromolecules at the surface of a polymeric solid have considerable mobility, and the specific arrangement of functional groups of macromolecules at the surface is dictated by the environmental conditions in which the surface is placed. Consequently, the change of environmental conditions, such as immersion in water or placement in a biological surrounding, could cause a considerable degree of change in the surface characteristics of a polymer from those evaluated in the laboratory against ambient air. The mobile nature of a polymer surface can be investigated by surface‐implanting fluorine‐containing moieties, mainly—CF3, by the plasma implantation technique and following the disappearance and …

River Discharge Study, Laughlin, Nevada: Colorado River Model And Diffusion Study, B. Dennis Hugh, David L. Stringfield, Jill C. Bicknell, Robert A. Ryder, Clark County Sanitation District, Nevada

Publications (WR)

A water quality modeling study of the Mohave Reach of the Lower Colorado River (from Davis Dam to the Nevada/California Stateline) was conducted to evaluate potential water quality impacts resulting from a proposed Laughlin, Nevada wastewater effluent discharge. The study included four major components: (1) review of the current regulatory framework; (2) a field data collection program to document existing water quality conditions in winter, summer, and fall; (3) development and verification of far-field and near-field (mixing zone) water quality models; and (4) application of the models to project future river quality conditions for several treatment-discharge alternatives as well as …

Limnological Monitoring Data For Lake Mead During 1987: Technical Report No. 20, Larry J. Paulson

Publications (WR)

Limnological monitoring was conducted in Las Vegas Bay and Boulder Basin from April to December of 1987. The purpose of the monitoring was to (i) document possible changes in water quality resulting from decreased phosphorus loading in Las Vegas Wash, and (ii) establish a data base for evaluating the adequacy of water quality standards.

Characterization Of The Lipopolysaccharides From Rhizobium Phaseoli Symbiotic Mutants, Francisca Garcia

Masters Theses

The lipopolysaccharides (LPSs) of the Rhizobium phaseoli CE3 and its mutants CE109, CE309 and the transconjugate Rhizobium leguminosarum LB2/109.11 were isolated and analyzed by gas chromatography (GC) and ¹H nuclear magnetic resonance (NMR) spectroscopy. CE3 is the wild type strain which is nodulation-proficient (Nod⁺). Strain CE109 and CE309 have a transposon, Tn5, inserted into Region I and Region III of their respetive chromosomes. Mutants CE109 and CE309 are defective in nodule development (Ndv^-). Transconjugate R. leg. LB2/109.11 has the DNA of the R. leg. LB2 wild type and also Region I portion of the CE109 …

A Study Of The Heterogeneous Electron Transfer And Dioxygen Binding Reactions Of Myoglobin, Bertha Bauer Cosby King

Theses and Dissertations

Quasi-reversible electron transfer kinetics are reported for sperm whale myoglobin reacting at tin-doped indium oxide electrodes. This reaction was studied by three different electrochemical or spectroelectrochemical methods; cyclic voltammetry (CV), single potential step chronoabsorptometry (SPS/CA) and derivative cyclic voltabsorptometry (DCVA). Kinetic parameters were determined from experiments which followed the purification of the protein,

the pretreatment of the electrode surface, and the removal of dioxygen from the sample solution. A formal heterogeneous electron transfer rate constant, k0′, of 2.6 (±0.5) x 10-5 cm/s and a transfer coefficient, α, of 0.48 (±0.05) were obtained using SPS/CA. These results are shown to correlate …

Incorporation Of A Product Of Mevalonic Acid Metabolism Into Proteins Of Chinese Hamster Ovary Nuclei, Michael Sinensky, L. A. Beck, T. Hosick

Faculty Publications, Biological Sciences

We have examined the nuclear localization of isoprenylated proteins in CHO-K1 cells labeled with [14C]mevalonate. Nuclear proteins of 68, 70, and 74 kD, posttranslationally modified by an isoprenoid, are also components of a nuclear matrix-intermediate filament preparation from CHO cells. Furthermore, the 68-, 70-, and 74-kD isoprenylated polypeptides are immunoprecipitated from cell extracts with two different anti-lamin antisera. Based on exact two-dimensional comigration with lamin B, both from rat liver lamin and CHO nuclear matrix-intermediate filament preparations, and its immunoprecipitation with anti-lamin antisera, we conclude that the 68-kD isoprenylated protein found in nuclei from [14C]mevalonate-labeled CHO cells is lamin B. …

Studies On The Effect Of Palmitylcarnitine Chloride On The Solubility Of Etoposide, Lola Kashyap

University of the Pacific Theses and Dissertations

The effect of an endoqenous surfactant, palmitylcarnitine chloride (PCC), on the solubility of etoposide was investigated. Preliminary studies were conducted to establish optimum experimental conditions for subsequent equilibrium solubility determinations. Infrared spectroscopy and thin layer chromatography techniques were used to establish the purity and identity of PCC. PCC was found to undergo rapid hydrolysis in aqueous solutions at 37.0° ± 0.5° C and the degradation was independent of concentration. The effect of pH on the stability of PCC was investigated. These studies revealed that PCC was most stable in the range pH 3.0 - 4.0. Etoposide was found to be …

Electrochemical And Surface Enhanced Resonance Raman Study Of Heme Proteins At Bare Metal Electrodes, David Edward Reed

Theses and Dissertations

Direct heterogeneous electron transfer reactions between horse heart cytochrome g_and silver electrodes were investigated by electrochemical and spectroelectrochemical methods. The kinetics of these reactions were established as being quasi-reversible, with a formal heterogeneous rate constant (k°'s,h) ranging between 0.18 - 1.5 x 10^-3 cm/s, for both polished and electrochemically roughened silver surfaces. Such reactions were stable and reproducible for over ten hours at room temperature. These results clearly demonstrate that neither electrode surface modification nor the inclusion of mediators is necessary to study electron transfer reactions of heme proteins at metal electrodes.

A crucial factor in obtaining the quasi-reversible …

River Discharge Study, Laughlin, Nevada: Field Survey Data, 1987, B. Dennis Hugh, David L. Stringfield, Jill C. Bicknell, Robert A. Ryder, Clark County Sanitation District, Nevada

Publications (WR)

A report of the first field data collection effort for the Laughlin River Discharge Study, conducted by Kennedy/Jenks/ChiIton in February, 1987, on the Mohave Reach of the Colorado River. This report also serves to transmit the laboratory analysis reports for all of the analyses performed and summary tables of the results. This report is organized as follows: 1. Field Conditions and Methodology 2. Summary of Sampling and Analysis Results 3. Deviations from the Proposed Sampling Program 4. Recommendations for Future Sampling 5. Attachments: A. Climatological Data B. Davis Dam Average Hourly Releases C. Laboratory Analysis Reports

Investigation Of Complex Formation By Oligomers Of Cytosine And Guanosine, Steven Roberts Davis

Chemistry & Biochemistry Theses & Dissertations

Duplex formation between oligo(C:G) _n where n=3 to 4 was shown not to occur under conditions favorable for duplex formation between poly G and poly C. Instead, a stable guano sine self-structure was found to form which a T_m of 50°C for (Gp)₃ and 80°C for (Gp)₄ at strand concentrations of 10^-5M in 1M NaCl. Neither a duplex nor a self-structure formed in the absence of salt.

Oligomers of guanosine and cytosine were obtained by basic hydrolysis and separated according to chain length using DEAE Sephadex column chromatography. Separation of cytosine oligomers with chain lengths …

Determination Of Netropsin-Dna Binding Constants From Footprinting Data, Brian Ward, Robert Rehfuss, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

A theory for deriving drug-DNA site binding constants from footprinting data is presented. Plots of oligonucleotide concentration, as a function of drug concentration, for various cutting positions on DNA are required. It is assumed that the rate of cleavage at each nucleotide position is proportional to the concentration of enzyme at that nucleotide and to the probability that the nucleotide is not blocked by drug. The probability of a nucleotide position not being blocked is calculated by assuming a conventional binding equilibrium for each binding site with exclusions for overlapping sites. The theory has been used to evaluate individual site …

Polymerization In Nonaqueous Lyotropic Liquid Crystals With A Polymerizable Solvent, Stig Friberg, Chang Sup Wohn, Frances E. Lockwood

Chemistry Faculty Research & Creative Works

Lamellar liquid crystals of lecithin and 2-hydroxyethyl methacrylate (HEMA) were polymerized by using UV radiation. Optical microscopy, infrared spectroscopy, and small-angle X-ray diffraction were used to compare the structure prior to and after polymerization. The lamellar structure was retained after polymerization with increased interlayer spacing. © 1987, American Chemical Society. All rights reserved.

Electron Transfer-Oxy Radical Mechanism For Anti-Cancer Agents: 9-Anilinoacridines, Peter Kovacic, James R. Ames, Michael D. Ryan

Chemistry Faculty Research and Publications

A possible mode of action involving electron transfer is advanced for the 9- anilinoacridines. The mechanism entails formation of toxic oxy radicals which destroy the neoplasm. Cyclic voltammetry was performed on iminium type ions derived by protonation of the acridines. Reductions were generally reversible with potentials of about - 0.60 V. Involvement of quinoidal metabolites is also a possibility. The relationship of electrochemical behavior to structure and physiological activity is addressed.

Reactions Of Organic N-Chloramines In The Gastric Fluid Of The Rat, Kathryn E. Mazina

Chemistry & Biochemistry Theses & Dissertations

Using chlorine as a drinking water disinfectant may have potential health effects due to its reactivity with organic amino nitrogen compounds found in the stomach. Organic N-chloramines have been shown to form in the stomachs of laboratory rats. The possible reactions of N-chloramines in the stomach fluid were examined in this study using a model radiolabeled N-chloramine. ³⁶Cl-N-Chloropiperidine, was synthesized and purified to remove ³⁶Cl-chloride. Stomach fluid was obtained from Sprague-Dawley rats which had been first fasted for 24 or 48 hours and then administered 3 mL of deionized water. Different concentrations of radiolabeled chloramine were reacted with …

Synthesis Of Potential Long Acting Calcium Channel Antagonists: A Study Of 1,4-Dihydropyridine Analogs, Thomas E. Christos

Chemistry & Biochemistry Theses & Dissertations

An investigation was undertaken to synthesize and evaluate longer acting analogs to the antihypertensive agent nifedipine. Analogs that are capable of covalent bonding to the nifedipine receptor were considered. These compounds may show increased activity as they will remain at the receptor for a longer period of time.

During the course of this study, previously unreported and unexpected products were encountered and lead to a more intense examination of the Hantzsch synthesis. Of particular interest was the oxazolidine 25 which was a major component of the Hantzsch synthesis when ethanolamine was used instead of ammonium hydroxide. Also isolated during this …

Lake Mead Cover Enhancement Project, Jennifer Stevens Haley, Suzanne Leavitt, Larry Paulson, Donald H. Baepler

Publications (WR)

Ninety-three wildlife agencies were surveyed for information on their attempts to improve fish habitat. In addition, an annotated bibliography including over 100 summaries was completed on: 1. largemouth bass cover requirements and preferences, 2. use and effectiveness of artificial cover, 3. aquatic plant introduction and species requirements for germination and establishment, 4. terrestrial plant introduction and species requirements for germination and establishment, and 5. nutrient exchange between sediment, aquatic plants, and water. A reconnaissance of existing terrestrial and aquatic vegetation was completed in June 1986 including the production of a video tape of the Nevada shoreline of Lake Mead. Cover …

Analysis Of Polycyclic Aromatic Hydrocarbon (Pah) In Stack Sample Particulates Formed During Waste Combustion ; Substituent Effects On The Strain Molecules, Ping Chiang Lyu

Theses

PART A: The total thirty samples came from wastes incineration of five industry companies in New Jersey have been examined. The EOM levels showed, especially for the less polar substances, lower than if they were collected at room temperature in the manner of ambient sampling. HPLC analyses of PAH, nitro-PAH and Quinone-PAH have been performed. Brief comparison is made with previous study.

PART B: Ab initio Molecular orbital calculations using the 3-21G basis set provide good approximations to the experimental geometries of substituted strained organic molecules. A series of disubstituted prismanes have been calculated at this level and the effects …

Effect Of Phosphate On The Kinetics And Specificity Of Glycation Of Protein, Nancy G. Watkins, Carolyn I. Neglia-Fisher, Daniel G. Dyer, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The glycation (nonenzymatic glycosylation) of several proteins was studied in various buffiner os rder to assess the effects of buffering ions on the kinetics and specificity of glycation of protein. Incubation of RNase with glucose in phosphate buffer resulted in inactivation of the enzyme because of preferential modification of lysine residues ino r near the activsei te. In contrast, in the cationic buffers, 3-(N-morpholino)propanesulfonic acid and 3-(N-tris(hydroxymethyl)rnethylamino)- 2-hydroxypropanesulfonica cid, the kineticso f glycation of RNase were decreased 2- to 3-fold, there was a decrease in glycation of active site versus peripheral lysines, and the enzyme was resistant to inactivation by …

The Aminolysis Of N-Hydroxysuccinimide Esters. A Structure-Reactivity Study, Gary W. Cline, Samir B. Hanna

Chemistry Faculty Research & Creative Works

Twelve amines, which vary substantially in basicity and in steric environment around N, have been allowed to compete—in anhydrous dioxane solution—in the aminolysis of the N-hydroxysuccinimide esters of unsubstituted, p-OCH₃, p-N0₂, and 3,5-(N0₂)₂ benzoic acids. The amines, which encompass a basicity range of 6.5 pk units, display a 10000-fold variation in reactivity in their reaction with the p-N0₂ester. for the sterically unhindered amines, a Bronsted-type plot of log k_obsdvs. pK_a has a slope of ~0.7. The data fit a model (Satterthwait, A. C.; Jencks, W. P. J. Am. …

Las Vegas Wash And Lake Mead Proposed Water Quality Standards: Revisions And Rationale, State Of Nevada: Division Of Environmental Protection

Publications (WR)

Rationale of review and for proposed changes to the Nevada Pollution Control Regulations (NAC 445.1354, 445.1355, 445.1356, 455.1367, 445.1352, 445.1353, 445.1350, 445.1351) before the State Environmental Commission on June 23 and 24, 1987.

Raw Nutrient Data, Leanna Gail

Publications (WR)

Data collected at various stations around Lake Mead. Includes information about substances present in various water samples.

The Preparation And Reaction Of Novel Glycosyl Ureas And Thioureas, Robert Scott Johnson

Masters Theses

No abstract provided.

Maine Acid Rain Study : Reports, Maine Department Of Environmental Protection

Maine Collection

Maine Acid Rain Study : Reports

Maine Department of Environmental Protection, Augusta, Maine (February, 1987).

Contents: Acid Rain Precursor Inventory and Evaluation / Modeled Sulfur Deposition in Maine / High Elevation Lake Monitoring in Maine

Determination Of Dissociation Energies And Thermal Functions Of Hydrogen‐Bond Formation Using High Resolution Ftir Spectroscopy, B. A. Wofford, M. E. Eliades, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A technique which employs high resolution Fourier transform infrared spectroscopy is demonstrated for evaluation of hydrogen bonddissociation energiesD ₀ and D _e . Results for HCN‐‐HF give a D ₀=20.77(22) and D _e =28.77(45) kJ/mol which are compared with previously determined values obtained from microwave absolute intensity measurements and a b i n i t i o molecular orbital calculations. Rovibrational band information available for HCN‐‐HF also permits evaluation of thermal functions of dimer formation in kJ/mol: ΔU ^○ _298.2 =20.1(2), ΔH ^○ _298.2 =22.6(2), ΔG ^○ _298.2 =59.4(2), ΔS ^○ _298.2 =−0.1235.