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The Determination Of Biological Activity And Biochemical Mode Of Action For The Oxadiazole And Diacylhdrazine Insecticides, Bonnie M. Gunn

Retrospective Theses and Dissertations

This report includes the determination of activity and possible mode of action for a group of potential new insecticides. The biological screening procedure was developed using Drosophila melanogaster as the test organism while Musca domestica was used for mode of action assays. The percent kill for each compound is based on the number of eggs placed on media containing the insecticide minus the number of adults enclosed as compared to the control media reared flies. Observations were made on all stages from eggs through adults to determine time of death and if any malformations were present. These observations aided in …

Comparison Of Proton Transfers In (S2h5)+ And (O2h5)+, L. Bigham, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The energetics and electronic rearrangements associated with proton transfer between S atoms in (H₂S–H–SH₂)⁺ are calculated using ab initio molecular orbital methods and compared with similar data in the first‐row analog (H₂O–H–OH₂)⁺. The full potential energy surface of (S₂H₅)⁺, calculated as a function of the H‐bond length as well as the position of the proton, contains two equivalent minima separated by a small energy barrier, whereas the surface of (O₂H₅)⁺ contains a single minimum corresponding to a symmetric …

Contribution Of Dispersion To The Properties Of H2s‐‐Hf And H2s‐‐Hcl, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out using a doubly polarized basis set. Dispersion, evaluated by second‐order Møller–Plesset perturbation theory (MP2), is found to have a profound influence on the stabilities and structures of the H‐bonded complexes. The contribution of dispersion to the H‐bond energies of H₂S‐‐HF and H₂S‐‐HCl is 44% and 69%, respectively, placing this attractive term second in magnitude only to electrostatics. Reductions of the intermolecular distance of 0.17 and 0.34 Å result from inclusion of correlation effects. Nevertheless, the influence of dispersion upon the angular characteristics of the …

Influence Of Basis Set On The Calculated Properties Of (H3n–Hcl), Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The structure of (H₃N–HCl) is investigated by ab initio calculations using a number of different basis sets ranging from minimal to split valence. The effects of including a diffuse sp shell and d orbitals on Cl are considered as well. The geometries of the complex and the isolated subunits are fully optimized. Minimal basis sets (STO‐3G, STO‐6G, and MINI‐1) lead to an overestimate of the interaction between the subunits. Addition of d functions produces only a marginal improvement. The 3‐21G, 3‐21+G, MIDI‐1, and LP‐31G split‐valence sets erroneously predict an ion pair …

Kinetics Of Reduction Of Cytochrome C Oxidase By Dithionite And The Effect Of Hydrogen Peroxide, M. Brunori, D. Bickar, J. Bonaventura, C. Bonaventura

Chemistry: Faculty Publications

The reduction of cytochrome c oxidase by dithionite was reinvestigated with a flow-flash technique and with varied enzyme preparations. Since cytochrome a3 may be defined as the heme in oxidase which can form a photolabile CO adduct in the reduced state, it is possible to follow the time course of cytochrome a3 reduction by monitoring the onset of photosensitivity. The onset of photosensitivity and the overall rate of heme reduction were compared for Yonetani and Hartzell-Beinert preparations of cytochrome c oxidase and for the enzyme isolated from blue marlin and hammer-head shark. For all of these preparations the faster phase …

Search For New Membrane Active Substances: Synthesis Of 3-Tropanols With Alkyl, Alkenyl And Alkenynyl Group At The Bridgehead, Ramalinga Murty Dharanipragada

Graduate Theses, Dissertations, and Problem Reports (ETD)

In recent years, Witkop and coworkers have isolated several structurally unique alkaloids from the colombian frog belonging to the genera Dendrobates. These alkaloids, which occur in the defensive skin secretions of the frog have been found to be highly active venoms as well as mucosal tissue irritants towards both mammals and reptiles. Among them are three important alkaloids histrionicotoxin, isodihydrohistronicotoxin and octahydrohistronicotoxin.

Racial Differences In The Distribution Of Posterior Circulation Occlusive Disease, Philip B. Gorelick, Louis R. Caplan, Daniel B. Hier, Dushyant Patel, Patricia Langenberg, Michael S. Pessin, Jose Biller, David Kornack

Chemistry Faculty Research & Creative Works

We Compared Clinical and Arteriographic Features in 27 White and 24 Black Patients with Symptomatic Posterior Circulation Occlusive Disease. the Degree of Arterial Stenosis Was Measured Independently by Two Examiners at 12 Sites within the Vertebrobasilar Territory. Racial Comparisons Were Made based Upon the Distribution of Extra- and Intracranial Occlusive Lesions and Symptomatic Sites of the Lesions. White Patients Had Significantly More Angina Pectoris, More Lesions of the Origin of the Left Vertebral Artery and More High-Grade Lesions of the Extracranial Vertebral Arteries. Black Patients Had Significantly Higher Mean Diastolic Blood Pressure, More Diabetes Mellitus, More Lesions of the Distal …

Interobserver Variability In The Assessment Of Neurologic History And Examination In The Stroke Data Bank, David Shinar, Cynthia R. Gross, Jay P. Mohr, Louis R. Caplan, Thomas R. Price, Philip A. Wolf, Daniel B. Hier, Carlos S. Kase, Irene G. Fishman, Christine L. Wolf, Selma C. Kunitz

Chemistry Faculty Research & Creative Works

Interobserver Reliability in Obtaining Neurologic Histories and Examinations Was Investigated among Neurologists Collaborating in the Stroke Data Bank (SDB). Seventeen In-Hospital Stroke Patients Were Examined by Six Neurologists Experienced in Stroke over the Course of Three Days. Patients Were Examined Twice a Day for Two Successive Days, with Each Patient Seen by Four Different Neurologists. Data Were Recorded on SDB Forms, According to Definitions and Procedures Established for the SDB. Percent Agreement and Κ Coefficients Were Calculated to Assess the Levels of Agreement for Each Item. Important Differences in Levels of Agreement Were Found among Items on Both Neurologic History …

Removal Of Colloidal Silica In Simulated Seawater By A Dynamic Multi-Short-Circuited Galvanic Cell, Jan E. Osterholm, Paul W. Kramer, Hlrotsugu K. Yasuda

Chemistry Faculty Research & Creative Works

A dynamic multi-short-circuited galvanic cell (MSCGC) with Pt-AI electrodes has been used to study the removal of colloidal silica from seawater as a pretreatment step for the desalination of seawater by use of reverse osmosis. The rate of silica removal is observed to be affected by the flow rate of the solution through the cell and the dissolved oxygen content of the solution as well as by the nature of the aluminum electrode surface and the number of contact points (short circuits) between the aluminum and platinum. The total silica content is reduced by 95 % by use of this …

Dynamic Structure Of N-Hexadecane Solubilized In A Nonionic Surfactant Bilayer Measured By Deuteron Magnetic Resonance, Anthony J.I. Ward, Stig Friberg, David W. Larsen, Shankar B. Rananavare

Chemistry Faculty Research & Creative Works

A 2H NMR study was made of the order parameters of n-hexadecane molecules solubilized up to 55% (w/w) in a lyotropic lamellar liquid crystal of tetra ethylene glycol n-dodecyl ether and water for a range of compositions of varying water and hydrocarbon content. The NMR data supported a model with only a small amount of penetration of the hydrocarbon between the amphiphilic molecules and a rapid exchange on the 2H NMR time scale between the penetrated segments and the nonpenetrating molecules which latter are essentially isotropic. © 1985, American Chemical Society. All rights reserved.

Translational Control By Adenovirus: Lack Of Virus-Associated Rna(I) During Adenovirus Infection Results In Phosphorylation Of Initiation Factor Eif-2 And Inhibition Of Protein Synthesis, John Siekierka, Thomas M. Mariano, Patricia Reichel, Michael B. Mathews

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

The dl331 mutant of adenovirus serotype 5 fails to produce virus-associated (VA) RNA(I), and cells infected with this mutant do not synthesize proteins efficiently at late times in infection. The translational defect occurs at the level of polypeptide chain initiation, and cell-free extracts prepared from dl331-infected cells exhibit the defect observed in vivo. Addition of either eukaryotic initiation factor 2 (eIF-2) or guanine nucleotide exchange factor (GEF) to these cell-free extracts restores translational activity, with GEF functioning more efficiently in this regard. These results suggest that cells infected with the dl331 mutant develop a translational block at the level of …

Chemical Studies On Oxomolybdenum(Vi,Iv) Complexes As Bioinorganic Models For The Molybdenum Oxidases, James Thomas Lyon Iii

Theses and Dissertations

The synthesis, characterization, and chemical properties of Mo(VI)o₂(5-X-SSP) and Mo(VI)o₂(5-X-SSE), (5-X- SSP²- = 2-((5-X-salicylidene)amino)benzenethiolate; 5-X- SSE^2- = 2-((5-X-salicylidene)amino)ethanethiolate; X = Br, Cl, H, CH₃O), which contain tridentate (ONS) Schiff base ligands is described. The chemical properties of these molybdenum complexes are compared with those which possess tridentate (ONO) Schiff base ligands. Cyclic voltammetry was used to obtain cathodic reduction potentials (E_PC) for the quasi-reversible reduction of the cis-dioxomolybdenum (VI) complexes. Although the reductions are quasi-reversible, trends are observed in E_PC both within series and when different series are …

Structure Of A Solvated Nickel(Ii) Complex Of (S)-2'-(N-Benzylprolyl)Aminoacetophenone And (R)-Valine Schiff Base, C25H29N3Nio3.1/2c4H8O. Conformational Calculation Of Diastereomeric Complexes Of (R)-Valine And (S)-Valine, Sergey V. Lindeman, T. V. Timofeeva, V. I. Maleyev, Yuri N. Belokon, M. G. Ryzhov, V. M. Belikov, Yuri T. Struchkov

Chemistry Faculty Research and Publications

No abstract provided.

Trans Diequatorially Fused 3',3'-Diphenyl-2'-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Glucose, Julian Guardado Puentes

University of the Pacific Theses and Dissertations

The chemistry of amino sugar compounds has been studied in the last years in connection with the study of natural products, and many of them have been isolated. ^57,17,18 Amino sugars play an important role in biochemistry, forming blocks of homo- and heteropolymers and complex molecules such as microbial polysaccharides, enzymes, gangliosides, glycoproteins, and antibiotics.

This research project had the purpose of preparing a derivative of 2-amino-2-deoxy-D-glucose, with a free hydroxyl group at the anomeric carbon, with the 4,6-positions blocked with the benzylidene cyclic acetal, and the 2,3-positions being blocked by a 3,3-diphenyl-2-morpholinone ring trans diequatorially fused to the amino …

Chapter 3 Coatings And Surface Modification Using Low Pressure Non-Equilibrium Plasmas, Harold F. Winters, Robert P.H. Chang, C. J. Mogab, John Evans, John A. Thornton, Hirotsugu Yasuda

Chemistry Faculty Research & Creative Works

No abstract provided.

Plasma Polymerization Investigated By The Substrate Temperature Dependence., H. Yasuda, Cheng Wang

Chemistry Faculty Research & Creative Works

In the reported experiments, plasma polymerization of tetrafluoroethylene (TFE), perfluoro-2-butyl-tetrahydrofuran (PFBTHF), ethylene, and styrene were investigated in various combinations of monomer flow rates and discharge wattages for the substrate temperature range of minus 50 to 80 degree C. The polymer deposition rates can be generally expressed by k//o equals Ae** minus **b**t, where k//o is the specific deposition rate given by k//o equals (deposition rate)/(mass flow rate of monomer), A is the preexponential factor representing the extrapolated value of k//o at zero absolute temperature, and b is the temperature-dependence coefficient. It was found that the value of b is not …

Heterocyclic Syntheses Utilizing Aryl Cyanates, Joseph Eugene Drumm

Masters Theses

No abstract provided.

The Application Of Multiderivative Infrared Spectroscopy To Iodine Number Determination, Jeffrey C. Lowry

Masters Theses

The Food and Drug Administration requires the disclosure of total unsaturation of commercial products as an indication of nutritional value. This unsaturation is a guide to the expected stability of food additives, such as edible oils and foods in which they are used. Unsaturation is typically evaluated as an iodine number, calculated for these additives based on their consumption of iodine through addition across the carbon-carbon double bonds. This titration method can typically take 45 minutes.

The investigation presented develops an alternative method for determining iodine numbers of some common oils using a computerized infrared spectophotometer. The analysis time, as …

The Kinetics Of The Metal Exchange Reaction Between N-(2-Hydroxyethyl) Iminodiacetatonickelate (Il) And Copper(Ii), Craig R. Weed

Masters Theses

The reaction between copper(II) and N -(2-hydroxyethyl)iminodiacetatonickelate( II) (NiHEIDA) was studied between pH 4.0 and 5.6 over a 70 fold variation in copper concentration at an ionic strength of 1.25 and a temperature of 25° C. The reaction order in both NiHEIDA and Cu(U) is first. The reaction rate is pH sensitive and a hydrogen dependent pathway as w ell as copper dependent and copper and hydrogen independent pathways were found.

Evidence is given for a stepwise mechanism for the unwrapping of HEIDA from its nickel complex, follow ed by copper attack to give a dinuclear intermediate, which then breaks …

Kinetics Of The Formation Of The Nickel(Ii) Complex With N, N' -Dimethylethylenediaminediacetic Acid And The Metal Exchange Reaction Between N,N'-Dimethylethylenediaminediacetatonickel(Ii) And Copper(Ii), Roger A. Karel

Masters Theses

The kinetics of the reaction of aquonickel (II) ion with N'N'-dimethlethylenediaminediacetic acid has been studied at 25°C and 0.1M iconic strength over a pH range of 6.0 to 9.3 using stopped-flow techniques. Formation reactions in all cases were first-order in Ni (II) and in ligand. The formation rate constant for the protonated and unprotonated species were evaluated and compared to their theoretical value. The rate-determining step is shown to be ring closure. A comparison of this system with other studies involving complexation of nickel (II) confirm the magnitude of the internal conjugate base effect and also shows a correlation between …

A Proposal To Fertilize The Overton Arm And Gregg Basin Areas Of Lake Mead, Larry J. Paulson

Publications (WR)

Several limnological studies have been conducted in Lake Mead during the past decade. The recent studies clearly show that most of Lake Mead is deficient in nutrients, especially phosphorus, and very low in productivity. The reservoir-wide average total phosphorus concentration for 1981 - 1982 was only 9 mg/m³. This is below levels found In most oligotrophic lakes and reservoirs. Algal biomass, as measured by chlorophyll-a, averaged only 1.5 mg/m³. That also places Lake Mead in the oligotrophic range. Transparency, as measured by a Secchi disc, averaged 9-5 m in Lake Mead during 1981-1982. That far exceeds …

Expression Of Epstein-Barr Virus (Ebv) Dna And Cloned Dna Fragments In Human Lymphocytes Following Sendai Virus Envelope-Mediated Gene Transfer, David J. Volsky, Thomas Gross, Faruk Sinangil, Charles Kuszynski, Ronald Bartzatt, Timothy Dambaugh, Elliott Kieff

Chemistry Faculty Proceedings & Presentations

Purified EBV DNA and cloned DNA fragments were trapped in Sendai virus (SV) envelopes during envelope reconstitution. The DNA-loaded reconstituted envelopes (RSVE/DNA) served as gene-transfer vehicles using the capability of RSVE to fuse with normal and tumor cells. The efficiency of RSVE-mediated EBV DNA transfer into lymphoid tumor cells and fresh human lymphocytes was 5-10% of the enveloped 3H-labeled EcoRI fragment B of EBV DNA. Purified intracellular EBV (B95-8 strain) DNA induced EBV nuclear antigen (EBNA) in 0.2-1% of human lymphocytes, transiently stimulated cellular DNA synthesis, but did not fully transform cells. Cloned Sal I F1 fragment [approximately equal to …

Characterization Of Glycated Proteins By 13C Nmr Spectroscopy, Carolyn I. Neglia, Helga J. Cohen, Albert R. Garber, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

13C NMR spectroscopy has been used to characterize Amadori (ketoamine) adducts formed by reaction of [2-13C]glucose with free amino groups of protein. The spectra of glycated proteins were acquired in phosphate buffer at pH 7.4 and were interpreted by reference to the spectra of model compounds, N alpha-formyl-N epsilon-fructose-lysine and glycated poly-L-lysine (GlcPLL). The anomeric carbon region of the spectrum (approximately 90-105 ppm) of glycated cytochrome c was superimposable on that of N alpha-formyl-N epsilon-fructose-lysine, and contained three peaks characteristic of the alpha- and beta-furanose and beta-pyranose anomers of Amadori adducts to peripheral lysine residues on protein (pK alpha approximately …

Evaluation Of Plasma Polymers Of Silanes As Adhesion Promoters For Organic Paint, Y. Matsuda, H. Yasuda

Chemistry Faculty Research & Creative Works

Plasma-polymerized coatings were prepared in a bell-jar-type reactor equipped with a magnetron system behind parallel aluminum electrodes using an a.c. source of frequency 10 kHz. Tetramethoxysilane, dimethyldimethoxysilane and hexamethyldisilane were used as monomers. Alkyd paint was coated on titanium plates onto which plasma polymer films had been deposited, to investigate the characteristics of the plasma-deposited films as adhesion promoters. The relationship between the adhesion strength for the paint and the conditions for the plasma polymerization was studied. The properties of the plasma polymers are dependent on the conditions of plasma polymerization manifested by two domains, namely the energy-deficient and the …

Preparation Of Gas Separation Membranes By Plasma Polymerization With Fluoro Compounds, H. Nomura, P. W. Kramer, H. Yasuda

Chemistry Faculty Research & Creative Works

Plasma polymerization coatings were applied for the preparation of gas separation membranes. Mainly fluoro compounds were used as coating materials. The membranes showed good separation characteristics with high flux for gaseous systems. The plasma polymerization composite parameter given by W/FM plays an important role in obtaining excellent separation characteristics. The correlation between the conversion rate DR/FM, where DR is the deposition rate of plasma polymer, and W/FM is useful to consider the plasma polymer character under the different plasma polymerization conditions (discharge power W and monomer flow rate F). The proper conditions for membrane preparation lie in the intermediate region …

26th Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 26th 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, August 7-8, 1984.

Impact Of Several Chemical And Physical Properties Of Two H-Coal Recycle Solvent Streams On Their Relative Solvent Quality, Joe Collins

Masters Theses & Specialist Projects

The purpose of this study was to follow the solvent quality curve of the recycle solvent streams of the H-Coal Pilot Plant run by Ashland Petroleum Company at Catlettsburg, Kentucky. This was done with the use of a microautoclave (shaker-bomb liquefaction unit). Several physical and chemical properties of these recycle oils were determined, and these values were correlated with the observed solvent quality. It is shown that the relative, solvent quality of these recycle oils correlate well with many of the chemical and some of the physical properties determined in this study.

Use Of Ft-Ir And Nmr Spectra Of The Thf Extracts Of Mid-Rank Bituminous Coals To Predict Plasticity, Samuel Adesoji Irefin

Masters Theses & Specialist Projects

Plasticity, which typically develops at 380-420°C, is a unique property of mid-ranked coals. The phenomenon of plasticity in coals has been known for a long time but is still poorly understood. Even among coals of identical subrank and chemical composition, large differences in plastic behavior are commonly encountered. Plastic coals go through a softening and swelling state upon heating before they resolidify. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place.

The coking ability of a coal can be directly related to the plasticity of the coal. In liquefaction reactions, plastic coals tend to …

Aromatic Amine--Haloboranes : Evidence For Trigonal Boronium Cations, Debra H. Reid

Master's Theses

In the last twenty years Lewis adducts of boron trihalides and mixed boron trihalides have been examined using nuclear magnetic resonance spectroscopy. The donor to which the boron trihalide attaches has generally been some type of amine (strong donor), though oxygen, sulfur, phosphorous, and other donors ahve also been studied. The boron trihalide portion serves as the Lewis acid. Various nuclei (1H, 13C, 15N, 11B, 19F) have been examined in such boron trihalide adducts and the general trend in signal position in all 5 nuclei observed is (in order of increasing downfield shift) BF3

The acid strength of the boron …

Naphthalene-2,3-Dialdehyde: A Synthon To 7,9-Polymethylene-8h-Cyclohepta[B]Naphthalene-8-One And A Study Of Their Aromaticity, Edward O. Crapps

Dissertations

This report describes the synthesis of naphthalene-2,3-dialdehyde, and an analytical method for determining its purity by thin layer chromatography. Subsequently, the dialdehyde was condensed with various cyclic ketones to generate a series of polymethylene bridged naphthotropones. It was found that planarity and aromaticity increase with the size of the methylene bridge, although, the bridge must contain six or more methylene groups for the latter to be true. The claim for aromaticity is supported by NMR and IR data, which indicates the positive charge for a perchlorate cation salt is delocalized over the naphthalene and tropone ring system. Furthermore, from the …