Digital Commons Network^™

A Re-Examination Of The Reactions Of Cyanide With Cytochrome C Oxidase, M. G. Jones, D. Bickar, M. T. Wilson, M. Brunori, A. Colosimo, P. Sarti

Chemistry: Faculty Publications

Experiments were performed to examine the cyanide-binding properties of resting and pulsed cytochrome c oxidase in both their stable and transient turnover states. Inhibition of the oxidation of ferrocytochrome c was monitored as a function of cyanide concentration. Cyanide binding to partially reduced forms produced by mixing cytochrome c oxidase with sodium dithionite was also examined. A model is presented that accounts fully for cyanide inhibition of the enzyme, the essential feature of which is the rapid, tight, binding of cyanide to transient, partially reduced, forms of the enzyme populated during turnover. Computer fitting of the experimentally obtained data to …

Comparison Of Three Methods For Sampling Fishes And Macroinvertebrates In A Vegetated Wetland, B. J. Freeman, H. S. Greening, J. Douglas Oliver

Faculty Publications and Presentations

Three methods of sampling fishes, two seining methods and a drop trap method, were evaluated in heavily vegetated freshwater habitats. The portable drop trap method, which utilized a 1 x 1 m-sq. trap, collected significantly more macroinvertebrates and fish per unit area than did the seining methods. The meter square drop trap offered the additional advantages of a greater number of animals per unit effort and an integrated sample of vegetation, macroinvertebrates and fish in a given area. A 90% (s.d.= 7.4%) recovery of tagged fishes released into the traps in different habitats showed the m2 drop trap to be …

Part I: The Synthesis Of Potential Agrochemicals. Part Ii: The Use Of Gold's Reagent As A Lynch Pin In The Formation Of Five And Six Membered Heterocycles, Keith F. Correia

Retrospective Theses and Dissertations

This research report focuses on two topics: the synthesis of potential agrochemicals and the use of Gold's reagent as a lynch pin to form five- and six-membered heterocycles. A diacyl hydrazide and two oxadiazoles are prepared for use as possible insecticides. Gold's reagent behaves as a one-atom and two-atom lynch pin when reacted with 1, 4- and 1, 5-dinucleophiles, respectively. Reaction conditions, interpretation of spectral data, and recommendations for further research are provided.

Carbon Monoxide-Driven Reduction Of Ferric Heme And Heme Proteins, D. Bickar, C. Bonaventura, J. Bonaventura

Chemistry: Faculty Publications

Oxidized cytochrome c oxidase in a carbon monoxide atmosphere slowly becomes reduced as shown by changes in its visible spectra and its reactivity toward oxygen. The 'autoreduction' of cytochrome c oxidase by this procedure has been used to prepare mixed valence hybrids. We have found that this process is a general phenomenon for oxygen-binding heme proteins, and even for isolated hemin in basic aqueous solution. This reductive reaction may have physiological significance. It also explains why oxygen-binding heme proteins become oxidized much more slowly and appear to be more stable when they are kept under a CO atmosphere. Oxidized α …

Lyotropic Liquid Crystals From Lecithin, Water, And Polyethylene Glycol, Magda El Nokaly, Stig Friberg, David W. Larsen

Chemistry Faculty Research & Creative Works

Lyotropic liquid crystals with lecithin as the amphiphile and with water/polyethylene glycol (PEG) solutions as the solvent were prepared with polyethylene glycol/water ratios from 182 to 0. The liquid crystals were lamellar and the interlayer spacing was independent of the solvent content for water/PEG ratios ≤1 but increased strongly with the water/PEG ratio. Higher ratios gave increased interlayer spacing with solvent content similar to the variation for liquid crystals with water as solvent but the absolute values of the spacing were higher. © 1984 Academic Press, Inc. All rights reserved.

Some Plant Leaves Have Orientation-Dependent Epr And Nmr Spectra, Douglas C. Mccain, Ted C. Selig, University Of Illinois At Urbana-Champaign, John L. Markey

Department of Chemistry: Faculty Publications

Proton nuclear magnetic resonance (¹H NMR) spectra of leaves from 50 plant species were obtained at a spectrometer frequency of 470 MHz. Water present in leaf samples gives rise to characteristic spectral patterns. Most species show only one broad ¹H NMR peak; however, the leaves of some plants display complex, orientation-dependent spectra in which a common three-line pattern is discerned. The pattern varies with the angle between the leaf surface and the external magnetic field. Proton relaxation measurements show the presence of at least two water compartments in the leaves. The compartments are responsible for different components …

The Synthesis Of Various Substituted 3-Amino-7-Hydroxy-2,2-Dimethyltetralins And Their Opioid-Related Activities, David Alan Lippman

University of the Pacific Theses and Dissertations

A series of aminotetralones and aminotetralins were synthesized from the common intermediate F, 3-amino-2,2-dimethyl-7-methoxy- 1-tetralone. The final compounds derived from F were simple substituted and/or reduced analogues. The products would allow a progressive structure activity relationship to be drawn based on pharmacological testing.

The common intermediate F was synthesized utilizing a six step procedure starting with p-methoxyphenylacetic acid. The overall yield from the precursor to the F:HC1 was 25%. Compound F was either O-demethylated to form 3-amino-2,2-dimethyl-7-hydroxy-l-tetralone (I) or was dimethylated on the amine and subsequently O-demethylated to yield the 3-dimethylamino-7-hydroxy-2,2-dimethyl-l-tetralone (J). The last major modification was the reduction of …

Totally Empirical Wavefunctions From X-Ray Diffraction Data, Martin Jeffry Goldberg

Dissertations, Theses, and Capstone Projects

The interpretation of coherent x-ray diffraction experiments by a quantum model is described. Adjusting the coefficients of an LCAO expansion to best fit measured Bragg intensities results in a totally empirical quantum wavefunction. The quantum model is compared to a multipole expansion. The constraints imposed by quantum mechanics are examined, and several methods of satisfying these constraints while best fitting a wavefunction to measured Bragg intensities are detailed. Application is made to beryllium metal, with a resultant fit R(,1) = .00249. Similar applications to graphite and diamond are outlined. The formalism is extended to explicitly include solid-state effects, and this …

Mechanism Of Translational Control By Partial Phosphorylation Of The Α Subunit Of Eukaryotic Initiation Factor 2, John Siekierka, Veeraswamy Manne, Severo Ochoa

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Catalysis of ternary complex formation by the GDP exchange factor (GEF), in the presence of Mg2+, is blocked by phosphorylation of the α subunit of the eukaryotic initiation factor 2 (eIF-2). We proposed earlier that this phosphorylation interferes with the interaction between eIF-2 and GEF (then termed ESP). If so, inhibition should be related to the extent of phosphorylation. However, work in other laboratories indicated that in fully inhibited, heme-deficient lysates only 20-40% of the EIF-2 is phosphorylated. To understand the nature of the molecular lesion in eIF-2-α phosphorylation we used a system of pure components in which the rate …

13C Nmr Investigation Of Nonenzymatic Glucosylation Of Protein, Carolyn I. Neglia, Helga J. Cohen, Albert R. Garber, Paul D. Ellis, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Nonenzymatic glucosylation of protein is initiated by the reversible condensation of glucose in its open chain form with the amino groups on the protein. The initial product is an aldimine (Schiff base) which cyclizes to the glycosylamine derivative. The aldimine can undergo a slow Amadori rearrangement to yield the relatively stable ketoamine adduct which is structurally analogous to fructose. 13C NMR has been used to characterize these early products of nonenzymatic glucosylation, using RNase A as a model protein. C-1 of the beta-pyranose anomer of the glycosylamine was identified at 88.8 ppm in the spectrum of RNase glucosylated approximately 1:1 …

Plasma Polymerization Of Tetramethyldisiloxane By A Magnetron Glow Discharge, Ashok K. Sharma, H. Yasuda

Chemistry Faculty Research & Creative Works

Plasma polymerization of tetramethyldisiloxane by a magnetron glow discharge was studied. The glow discharge was created between parallel electrodes with a 10 kHz electric power source with a superimposed magnetic field using permanent bar magnets. Polymers were deposited onto moving substrates placed on the surface of a rotating disc located in between the electrodes. The deposition rates were determined with a quartz crystal thickness monitor placed on the plane of the rotating disc and just outside the edge of the disc. The current-voltage relationship observed for plasma polymerization of the monomer depends on the monomer feed rate and the conditioning …

Cationic And Anionic Micellar Catalyzed Hydrolysis Of Hydroxamic Acids, Douglas Eugene Conran

Masters Theses

The hydrolysis of octanohydroxamic and N-methyloctanohydroxamic acids in the presence of cationic and anionic micelles was investigated. Rate constants were determined for the hydrolyses in cetyltrimethylammonium bromide (ctab), the cationic surfactant, with 0.1111 N NaOH and in sodium 1-dodecanesulfonate, the anionic surfactant, with 0.09270 N HC1 at 50.01 + 0.11°C. The acid hydrolysis and the base hydrolysis of N-methyloctanobydroxamic acid followed the standard model for micellar catalysis.

Determination Of N,N'-Diphenylguanidine In Biological Tissues And Fluids Using High Pressure Liquid Chromatography, Edward Sidney Hunter Iii

Chemistry & Biochemistry Theses & Dissertations

N,N'-Diphenylguanidine (DPG) is a potentially toxic compound used in the vulcanization of rubber products. Distribution of DPG in hybrid mice (C57BL/6J interbred with DAB₂) was determined following intraperitoneal injection. Urine, fecal material, whole blood and tissues were collected at various times after administration of DPG and the extracts analyzed for DPG by high pressure liquid chromatography. Recovery of DPG from spiked urine and whole blood exceed 90%, however, the recovery of DPG from spiked tissue samples was approximately 70%.

DPG concentration in whole blood reached a maximum within ten minutes and rapidly decreased through 180 minutes after administration …

Part I: The Synthesis Of New Potential Insecticides. Part Ii: New Aromatic Nucleophililic Subsitution Reactions, Fluoroalkoxylation And N,N-Dimethylamination, Cesar Colon

Retrospective Theses and Dissertations

A series of routes are described for the synthesis of new potential insecticides which are symmetrical or asymmetrical similogs of 2,5-Bis (dichloropheny1)-1,3,4-oxadiazole and its precursor diacyl hydrazine. Also two new aromatic nucleophilic substitution reactions are discussed. Activated aryl halides are reacted with fluorinated alkoxide anions. In all cases, substitution of the halogen by a fluoroalkoxy group was observed, and activated aryl halides are reacted with HMPA as an N, N-dimethyl aminating agent. In all cases, substitution of the halogen by a dimethyl amino group was observed. The effect of the activating group and the leaving group is described and a …

Structural Changes Induced By Addition Of A Hydrocarbon To Water/Amphiphile Mixtures, H. Sagitani, Stig Friberg

Chemistry Faculty Research & Creative Works

The phase conditions in a system of water, hexadecane, sodium dodecyl sulphate, and di-ethylene glycol dodecyl ether showed the W/O microemulsions to be obtained first after destabilization of a liquid crystalline phase by addition of the hexadecane. The original lamellar liquid crystalline phase was moved towards higher surfactant/cosurfactant ratios and a new phase with inverse amphiphile cylinders in a hexagonal packing appeared. © 1983 Steinkopff.

The Synthesis Of Potential Insecticides: Haloalkoxy Phenyl Diacylydrazines And 1,3,4-Oxadiazoles, Kathleen S. Gibbs-Rein

Retrospective Theses and Dissertations

The syntheses of two classes pf compounds, diacylhydrazines and 2,5-disubstituted 1,3,4-oxadiazoles, intended for subsequent investigation of pesticidal activity are discussed. The experimental conditions and procedures necessary for the preparation of these potential insecticides are also revealed. Finally, spectral data are interpreted and explained, and recommendations for further research are given.

Synthesis Of Potential Agrochemicals And Reactions Of Vinamidinium And Azavinamidinium Salts With Organometallic/Borane Reagents And Activated Nitrales, Charles N. Moorefield

Retrospective Theses and Dissertations

This report discusses research which was conducted in two areas: the synthesis of potential agrochemicals and the study of vinamidinium and azavinamidinium salt chemistry. Four classes of compounds were synthesized and characterized in the study of new potential agrochemicals. These compounds include diacylhydrazines, semicarbazides, 2,5-disubstituted-1,3,4-oxadiazoles and bis-2,5-disubstituted-1,3,4-oxadiazoles. The reaction of [3-(dimethylamino)-2-azaprop-2-en-1-ylidene] dimethylammonium chloride (Gold's reagent) with organometallic/borane reagents was examined in efforts to find convenient syntheses for N,N-dimethylamino substituted alkyl and aryl compounds. Additionally, the reaction of 1,5-diazapentadienium chloride (Nair's reagent) with nitrile activated alkanes was examined to find a convenient synthesis of 3-substituted pyridines. Subsequent intramolecular ring closure of …

Electrical Properties Of Plasma-Polymerized Thin Organic Films, Maciej Gazicki, H. Yasuda

Chemistry Faculty Research & Creative Works

The electrical properties of plasma-polymerized films are summarized and compared to those of conventional polymers. Particular attention is devoted to the dielectric relaxation, dielectric breakdown, electric conductivity and photoconductivity, and their control via control of the plasma parameters. © 1983 Plenum Publishing Corporation.

Nonenzymatic Glucosylation And Glucose-Dependent Cross-Linking Of Protein, Albert S. Eble, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

A model system using RNase A has been established for studying the nonenzymatic glucosylation and glucose-dependent cross-linking of protein (Maillard reaction) under physiological conditions in vitro. The rate of glucosylation of RNase was first order in glucose. Glucosylation was accompanied by a comparable decrease in primary amino groups in the protein and lysine recoverable by amino acid analysis. Analysis of glucosylation reaction mixtures by sodium dodecyl sulfate-polyacrylamide gel electrophoresis in the presence of mercaptoethanol revealed the time-dependent formation of RNase dimer and trimer. The polymerization reaction was mixed order with respect to glucose concentration, but was approximately first order with …

The Combined Effect Of Cu And Zn On Selenastrum Capricornutum, Helmer Colonia-Roque

Dissertations and Theses

It has been demonstrated that the toxicity of heavy metals depends on their chemical speciation and can be related to their free ion activities, rather than the total metal concentrations. The objective of this study was to determine the effect of combined free ions of zinc and copper on the toxicity to the green alga Selenastrum capricornutum. This alga was grown in a defined medium, under controlled laboratory conditions, with a varying range of zinc and copper concentrations. The growth rate of the alga was inhibited at pZn = 5.93 or at pCu = 7.24. The results suggest that …

Cell-Mediated Immunity Of The Dog Lung And Effects Of Inhaled 239puo2 Or Pulmonary Tumors, Jennifer Baker Galvin

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Cell-mediated immunity (CMI) in the lung has not been well characterized due to the lack of applicable tests. A major objective was to define pulmonary CMI serially in immunized and control lung lobes using the leukocyte procoagulant (LPCA) assay in young adult dogs. This was compared to a standard, but less reproducible CMI assay, macrophage migration inhibition facet (MIF). The CMI response, as measured by the LPCA assay, peaked in the blood 7 days after lung immunization. The pulmonary CMI response measured with cells obtained by bronchial lavage from the immunized and control lung lobes peaked at 9 to 12 …

Studies In Peptide Synthesis Towards The Lanthionine Analog Of Des-N-Tetramethyl Triostin A, Ganesh Devdas Kini

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Studies have been carried out towards the synthesis of bicyclic octadidepsipeptide lanthionine 4, an analog of des-N-tetramethyl triostin A. Starting with a symmetrical lanthionine unit 5 (R₁, R₃ = Me; R₂, R₄ = t-butyloxycarbonyl), synthesized from the corresponding cystine by contraction with hexaethylphosphorus triamide, linear octadidepsipeptides 29 and 32 were synthesized.

Attempted cyclizations of 29 and 32 to the bicyclic octapeptide were unsuccessful.

The failure of the symmetrical approach to 4 prompted the synthesis of an unsymmetrical lanthionine unit with appropriate compatible protecting groups. Attempts to synthesize unsymmetrical lanthionines by nucleophilic displacement on …

Fluorine, Richard H. Langley, Larry Welch

Faculty Publications

Considering the long time in which fluorine compounds have been used it seems rather surprising that it was not isolated as an element until 1886. This long delay was not due to lack of effort, but to the reactivity of fluorine and the hazards of working with it and many of its compounds.

Preliminary Rovibrational Analysis Of The Nν6+Ν1−Nν6 Vibration In Hcn⋅⋅⋅Hf, E. Kyrö, K. Mcmillan, M. Eliades, D. Danzeiser, P. Shoja-Chaghervand, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

A preliminary rotation‐vibration analysis of the n=0 and n=1 subbands associated with the nν₆+ν₁−nν₆ hydrogen‐bonded vibration in HCN⋅⋅⋅HF has been completed. The following excited staterotational constantsB′ and band origin frequencies ν₀ have been determined for the complex. The results are consistent with a rotation‐vibration interaction constant α₁=−68.3±1 MHz which correlates with an excited stater(N⋅⋅⋅F) internuclear distance of 2.762 Å, a decrease of 0.034 Å relative to the ground state.Excited state lifetimes associated with assigned transitions are demonstrated to be …

Chemistry, Norman Kulevsky

UND Departmental Histories

This departmental history was written on the occasion of the UND Centennial in 1983.

The Phosphacylium Ion: Evidence For Its Existence As An Intermediate In Reactions Of Organophosphates, Thomas D. Matus

Electronic Theses and Dissertations

Prior to this work, no strong evidence existed which unequivocably proved the existence of phosphacylium ions as intermediates in reactions of this type. It is the object of this study to look into nucleophilic substitution at phosphorus, and the intermediates of these possible dissociative type reactions.

Intermolecular Interactions For Phosphatidyl Choline And Phosphatidyl Ethanolamine, Tony Flaim, Stig Friberg, Patricia L.M. Plummer

Chemistry Faculty Research & Creative Works

Intermolecular interaction between pairs of methylphosphocholine (MPC) and methylphosphoethanolamine were calculated using an extended CNDO/2 program. Experimentally determined conformations were used for the ethanolamine and choline groups. In the methylphosphocholine the major interaction was intramolecular, involving the phosphate ester-choline groups, while in the ethanolamine the maximum attraction was intermolecular between the ethanolamine and the phophate ester of a neighboring molecule(s). © 1983.

Preparation Of 2,5-Diaryl-1,3,4-Oxadiazoles, Joachim D. Dobe

Retrospective Theses and Dissertations

This report regards the research conducted in the synthesis of 2,5-disubstituted-1,3,4-oxadiazoles as potential insecticides which are closely related to the known insecticide DOWCO 416^R, 2,5-bis(2,4-dichlorophenyl)-1,3,4-oxadiazole. The following compounds were synthesized: 2-(2,4-dichloro-5-nitrophenyl)-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole, (2-(2,4-dichloro-5-nitrophenyl)-5-phenyl-1,3,4-oxadiazole, 2-(2,4-dichloro-5-aminophenyl)-5-aminophenyl)-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole and 2-(2,4-dichloro-5-aminophenyl)-5-phenyl-1,3,4-oxadiazole.

From the commercially available starting material, 2, 4-dichlorobenzoic acid, preparation of the above compounds involved nitration, reduction, esterification, preparation of monoacylhydrazines, preparation of substituted diacylhydrazines and preparation of 2, 5-disubstituted-1, 3, 4-oxadiazoles. All these compounds were characterized via NMR and infrared spectroscopy. In addition, this report includes discussion and recommendations concerning the experimental procedures and conditions for the preparation of these compounds.

The Effects Of Impoundments On Salinity In The Colorado River, Larry J. Paulson, John R. Baker

Publications (WR)

The increase in salinity of our western rivers has been identified as one of the most serious water quality problems in the nation. This is of special concern in the Colorado River where salinity has increased from pristine levels estimated at 380 mg/1 to present-day levels of 825 mg/1 at Imperial Dam. Flow depletions, associated with decreased runoff and increased evaporation and diversions, coupled with high salt loading from natural and man-created sources are considered the primary causes for rising salinity in the river. The urban and agricultural development projected to occur in the basin through this century could deplete …

Microcomputer-Assisted Colorimetric Determination Of Iron, A. M. Hoyt Jr.

Journal of the Arkansas Academy of Science

No abstract provided.