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The Intramolecular Torsional Potential And Dielectric Properties Of 2,3-Butanedione, Gevert H. Meyer

Masters Theses

Dipole moment measurements have been carried out on 2,3-butanedione in solution, pure liquid, and the vapor phase. A dipole moment of 1.03 ± .01 Debye was observed for dilute solutions of 2,3-butanedione in carbon tetrachloride. Pure liquid samples exhibit an anomalous dipole of 1.56 ± .01 Debye. The following results were obtained for vapor phase measurements: 1.04, 1.07, 1.08, 1.11, and 1.17 ± .01 Debye at 310.15, 350.15, 370.15, 431.70 and 472.10 ± .02°K respectively.

The acetyl torsional potential was characterized from the observed temperature dependence of dipole moment. This torsional mode was described by a two-parameter potential function: V(Ø) …

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclopropyl Derivatives, Lailing Magdalene Soong

Masters Theses

A second order nucleophilic substitution reaction with retention of configuration is predicted by Ugi and co-workers if electrophiles such as cyclopropyl, cyclobutyl, or cyclopentyl derivatives undergo substitution under conditions where the S_N2 process is faster than the competing S_N1 process.

A synthesis of both cis and trans-7-chlorobicyclo [4.1.0] heptane from olefin and dichlorocarbene is described. The compound, bicyclo [4.1.0] heptylpyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(III), which contains an alkylcobalt σ-bond, is obtained from the reaction of pyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(I) and 7-chlorobicyclo [4.1.0] heptane. The great light sensitivity of this compound has prevented its isolation in purity sufficient for nmr …

Studies Of Acetylcholinesterase In Synaptosomes, Syed Abbas Rizvi

Masters Theses

Acetylcholinesterase from rat brain was studied in crude homogenates, partially purified enzyme fractions, and in synaptosomes, to observe modification of the enzyme as a consequence of the modification of the membrane containing it.

Sodium dodecyl sulfate decreases the absorbance due to particles in the homogenate. This change in absorbance was proportional to both the concentration of sodium dodecyl sulfate and the concentration of the particles. Further, sodium dodecyl sulfate caused sulfhydryl groups to appear in the crude homogenate and in partially purified enzyme fractions. Synaptosomal preparations did not give such results. At concentrations of sodium dodecyl sulfate sufficient to cause …

Zwitterionic Carbonyl Halide Complexes Of Tungsten, Dragoslav Marcovich

Masters Theses

The first carbonyl halide zwitterionic complexes have been synthesized and are of the type cis- (OC)₄XWPPh₂(CH₂)nPPh₂R in which X is Cl, Br, or I, n is 1 or 2, and R is an alkyl group. The complexes were prepared by the reaction […]. The temperature of the reaction must be carefully controlled since the decomposition point of the product is only 10°C higher than that of the reactant.

The zwitterionic complexes are sensitive to light in solution but are insensitive to light in the solid state. Unlike carbonyl halide complexes of the …

Locating The St. Louis Urban Plume At 80 And 120 Km And Some Of Its Characteristics, J. F. Stampfer, J. A. Anderson

Chemistry Faculty Research & Creative Works

The feasibility of locating the urban plume of a moderately large urban area, as far as 120 km downwind, is shown. The method utilizes a single engine aircraft and aerosol instrumentation. A summary of the data obtained from 34 flights, during an 8-month period, is presented and the problems involved in interpreting the data are discussed. These difficulties include nonuniform background levels outside the plume, changing relative humidity, low wind speeds and stable atmospheric layers. The plume was characterized by concentrations of small particles (0.15 < r < 0.3 μm) ca. 1.5 times that in background air and concentrations of large particles (0.3 < r < 1.3 μm) usually greater than twice that in the background. The ratio of the concentrations of small particles to large particles in the plume was about one-half of that in the background. © 1975.

A Piagetian Approach To General Chemistry, Donald W. Beistel

Chemistry Faculty Research & Creative Works

No abstract provided.

Attempted Synthesis Of 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane, Kenny Uzoma Acholonu

University of the Pacific Theses and Dissertations

The purpose of this work was to investigate a general synthetic route to 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane.

Reductive Cleavage Of N-Substituted Benzenesulfonamides And P-Sulfamylbenzoic Acid, Robert E. Davenport

University of the Pacific Theses and Dissertations

The objective of the present work was to study further the effect of varying substituents on the nitrogen atom and on the ring of sulfonamides in the Birch reduction of aromatic sulfonamides, especially with respect to the amount of thiol formed, in the hope that information concerning the initial cleavage step might be discerned.

Gas Phase Hydrogen Bonding Infrared Studies Of Four Simple Alcohols, Lawrence John Anderson

Dissertations and Theses @ UNI

The purpose of this study was to develop methods for studying gas phase hydrogen bonding and to obtain evidence of the gas phase self association of methanol, ethanol, 2-propanol and 1-propanol. A gas sample transfer manifold was designed and constructed. The gas -1 8 -1 phase infrared spectra from 3050 cm to 3800 cm of methanol, ethanol, 2-propanol and 1-propanol were examined at low and saturated pressures at approximately 4o0 c. The measured integrated absorption areas of the methanol spectra were compared to areas calculated from results found in the literature. The areas were found to be in reasonable agreement …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Methyl Proton Nmr Shifts Of Coordinated Methanol In A Series Of Co(Ch,0h),X2+ Compounds, J.R Vriesenga, Jerry Goodisman

Chemistry - All Scholarship

The isotropic contact NMR shifts of the coordinated cis and tram methanol methyl proton resonances of a series of Co(CH30H)5X2+ complexes were measured, where the ligand X was pyridine, /I- and a-picoline, DMF, DMSO, acetonitrile, and water. The question of how to separate the observed shifts into their respective Fermi contact and dipolar (pseudocontact) contributions was examined in detail with the result that a new procedure for carrying out the separation was proposed. The dipolar shifts for these complexes were found to vary widely, with the acetonitrile complex exhibiting the largest dipolar shift. For the DMSO and water complexes the …

Syntheses And Characterizations Of Vanadyl (Iv) Complexes With Dihydroxydicarboxylate Ligands, Sharon K. Hahs

Chemistry and Chemical Biology ETDs

Binuclear complexes of the vanadyl(IV) tartrates have already been shown to exist both in the solid state and in solution. These complexes consist of two vanadyl(IV) ions bridged by two tartrato(4-) ligands, either of the same--DD (or LL)-- or opposite--DL--enantiomeric configuration. (The meso isomer of tartaric acid will not form binuclear complexes with vanadyl(IV).) The DL complex is more stable than the DD complex due to a greater degree of staggering between the vicinal hydrogen atoms on each tartrate chain. Investigations of vanadyl(IV) complexes with substituted tartaric acid ligands--specifically, (±)-dimethyltartaric acid and (±)-threomethyltartaric acid--have been undertaken to determine whether this …

Esterase Activity In The Greater Wax Moth Larvae, Daphne Lin Pai

Masters Theses & Specialist Projects

Some properties of esterases of the greater wax moth larvae, Galleria mellonela (L.), were examined and the enzymes partially purified. Several buffer systems were tried and it was found that tris buffer was most suitable. The tris buffer resulted in less hydrolysis of the acetylsalicylic acid. Esterase activity was determined with acetylsalicylic acid in tris buffer, pH = 7.85, 0.05 M. The enzymes were partially purified by combination of acetone powder preparations, ammonium sulfate precipitations and gel filtration.

The ratio of esterase activity to protein content was increased 1.03 fold by acetone powder preparation and 1.5 fold by 70% ammonium …

Photochemistry Of Beta-Methyl-Beta-Nitrostyrene & Its Derivatives, Donald Tang

Masters Theses & Specialist Projects

A series of β- methyl-β-nitrostyrenes have been synthesized and subjected to ultraviolet irradiation. A new technique has been developed for synthesis of 1-phenyl-1,2-propanedione-1-oxime and its derivatives by irradiation of the corresponding styrene. The yields of the oximes were almost quantitative [except 1-(p-nitrophynyl)-1,2-propanedione-1-oxime and 1-(m-nitrophenyl)-1,2-propanedione-1-oxime]. It has been found that irradiation of the appropriate styrene is a very simple, efficient, and general procedure for the synthesis of 1-phenyl-1,2-propanedione-1-oxime and a number of its derivatives. A number of derivatives of β- methyl-β-nitrostyrene (p-CH₃, p-Ch₃0, p-Cl, p-No₂, and m-NO₂) were irradiated. It was found that …

Asymmetric Induction In Grignard Reactions In A Chiral Solvent, John E. Davis

Dissertations

No abstract provided.

The Development Of An Arsenic(V) Selective Electrode, Sandra Gee Kang

Dissertations and Theses

The object of this research was to develop an arsenic(V) selective electrode. The electrode is based on a solid state membrane prepared by pressing a precipitate of silver arsenate-silver sulfide into a pellet. After the electrode was made, experiments were designed to check for three general characteristics of the electrodes: dependence of potential on pH for constant arsenic(V) concentration; dependence of potential on arsenic(V) concentrations at constant pH and extent of interference due to phosphate and arsenic(III) ions. From these measurements, it was found that Ag₂HAs0₄ was formed originally in the membranes containing a small fraction of …

Erratum: On Improved Wkb (Uniform Asymptotic) Quantum Conditions, Dunham Corrections, The Langer Modification, And Rkr Potentials, Russell T. Pack

Faculty Publications

In Eqs. (28) and (29) p should be changed to t.

Electrochemical Investigations Of The Mechanisms Of Reduction Of Benzaldehyde Compounds In Sulfolane, Neal Russell Armstrong

Chemistry and Chemical Biology ETDs

The mechanisms of the reduction of benzaldehyde and several sub­stituted benzaldehydes in the dipolar, aprotic solvent sulfolane, have been investigated. A combination of cyclic voltammetry, transmission spectroelectrochemistry and ring-disk voltammetry was used in this study. Cyclic voltammetric studies indicated that the one-electron benz­aldehyde reduction was followed by a dimerization of the radical anion intermediate to the pinacol. The reduction peak potentials of the benzaldehydes were cathodically shifted in sulfolane compared to values obtained in aqueos media. This indicates an increase in the benzaldehyde reduction energy in the aprotic solvent. The rate of the following chemical reaction was also slower than …

The Thermal And Photolytic Rearrangements Of Isatoic Acid Diazide, Ana Alejandre Ciereszko

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research has been the thermolysis and photolysis of isatoic acid diazide 1. Thermolysis in low boiling solvents produced the acylazido benzimidazolone 10, while refluxing in high boiling solvents gave rise to the imidazoindazoline 31, presumably via Curtius rearrangements.

Photolysis of the diazide in methylene chloride gave rise to two photo products, 10 and 31, while photolysis in tetrahydrofuran produced only 31.

A study of the spectral and chemical characteristics of these products have been carried out.

The Purification And Characterization Of Methylmalonyl Coa Mutase From Bovine Brain, Damon Martin

Theses and Dissertations

Methylmalonyl CoA mutase has been purified over 2300-fold from bovine brain using fractional precipitation, ion exchange resins, and gel filtration procedures. The crude extract had an equal mixture of mutase in the halo- and apoenzyme form. After the final purification step the ratio had changed to 86% holo-enzyme and 14% apoenzyme. The mutase enzyme had a pH optimum of 7. 0 in Tris-HCI buffer. The Km values for L-methylmalonyl CoA and succinyl CoA were 7.7 x 10^-4 M and 1.8 x 10^-4 M respectively. The equiIibrium constant in the direction of succinyl CoA formation was 19. Inhibition with N-ethylmalei-mide was …

Characterization Of Zinc-Containing Metalloproteins By Resonance Raman Spectroscopy, Robert Edward Derry

Dissertations and Theses

Cobalt-substituted carboxypeptidase and carbonic anhydrase were chosen as candidates for resonance Raman spectroscopy because they possess visible absorption due to the Co(II)-protein complex. However, no evidence for resonance-enhanced peaks due to the cobalt-containing chromophore was found with laser excitation near the visible absorption bands (514.5 nm) or closer to the ultraviolet absorption bands (457.9nm).

Arsanilazocarboxypeptidase and model azotyrosine compounds were selected for a Raman spectroscopic investigation because they have intense absorption bands in the visible region. All of these substances yielded similar resonance Raman spectra. Although there was no evidence for specific zinc-ligand vibrations, shifts in vibrational frequencies of the …

Restrictions On The Potential And Cross Section For Collisions Between Rigid Rotors, Louis Biolsi Jr.

Chemistry Faculty Research & Creative Works

A restricted distorted-wave treatment of the total cross section when two rigid diatomic molecules with orbital and nuclear spin angular momenta collide is examined. There are certain restrictions on the intermolecular potential and on the possible combinations of the various quantum numbers. These restictions are examined for the lowest order nonspherical elastic and the lowest order inelastic contributions to the total cross section. The effects of degeneracy averaging and of collisions between indistinguishable molecules are also briefly examined.

Alumina-Catalyzed Cope Rearrangement, Paul Jhy-Shing Wang

Dissertations and Theses

The alumina-catalyzed Cope rearrangements of meso- and dl-3,4-diphenylhexa-1,5-diene were examined in detail, following up a preliminary observation by H. Berg at Portland State University. Commercial column-chromatography grade alumina was employed, and was further activated before use by heating at 650-700° for four hours.

Using a ratio of 20 mg of dl-3,4-diphenylhex-l,5-diene to 1 g of alumina in heptane, the Cope rearrangement was complete within 15 minutes at room temperature to give exclusively trans,trans-1,6-diphenylhexa-1,5-diene. This was identified.by melting point, infrared spectroscopy and vapor phase chromatography.

The catalyzed rearrangement of meso-3,4-diphenylhexa-l,5-diene was run using the same diene …

16th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Final program and abstracts from the 16th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 5-6, 1974.

The Attack Of Hard And Soft Nucleophiles On 6-Methylsulfonyl-, 6-Methylsulfinyl-, And 6-Methylthioaminopteridines, William David Johnston

Theses and Dissertations

In an attempt to prepare 6-anilino and 6-benzylaminopteridines, 2,4,7-triamino-6-methylsulfonyl and 2,4,7-triamino-6-methylsulfinylpteridines were prepared and reacted with a number of benzylamines and aniline. These hard nucleophiles gave amine exchange products with no displacement at the 6 position. Aliphatic amines gave exchange in the 2,4-and 7-positions. The exchange occurring in the 7-position must be occurring by an AE mechanism. This is the first such exchange reported in a ring other than a 1,3-azine. Aniline gave no exchange product except in an acid catalyzed reaction, and then gave exchange in only the 2 and 4-positions. Numerous reactions on related substrates, are reported. Soft …

Part I. Catalytic Hydrocarbon Reforming By Technetium Catalysts.|Npart Ii.|Pacetone Azine And 3,5,5-Trimethyl-2-Pyrazoline Adducts Of Palladium Chloride, James Lynn Palmer

Theses and Dissertations

Technetium catalyzes hydrocarbon reforming reactions of dehydrocyclization, isomerization, hydrogenolysis, and coke formation. A kinetic equation was derived and E_a and A_o evaluated for dehydrocyclization of n-heptane, isomerization of n-pentane, and dehydrogenation of methylcyclohexane and cyclohexane. The results were related to the metal, the form of the catalyst, catalyst support, and the deactivation of the catalyst. The effect of sulfur compounds was determined. No residual radioactivity in the product was observed. The ligands, acetone azine (AA) and 3,5,5-trimethyl-2- pyrazoline (Py), reacted with (C_6H_5CN)_2PdCl_2 to form adducts, L_2PdCl_2 and (LPdCl_2)_n. Their structures were characterized by spectroscopic methods and some molecular weights determined. …

Thermodynamic Stability Constants Of Silver Bromide Complexes In Water And Water-Acetone Mixtures Determined By Ion-Selective Electrode Measurements, Arthur Lee Cummings

Theses and Dissertations

Thermodynamic equilibrium constants for silver(I) bromide complexes were determined by ion-selective membrane electrode potential measurements in water and in mixtures of water and acetone of approximately 5, 10 and 15 percent acetone by weight. Values of the solubility product constant were determined in each solvent system by calibration of a silver bromide membrane electrode with silver nitrate solutions and with sodium bromide solutions. Stability constants of silver(I) bromide complexes were determined using a silver ion-selective, silver sulfide membrane electrode in unsaturated solutions in which the formal concentrations of silver(I) and of bromide ranged from approximately I x 10-8 to 7 …

A Remote Aerosol Sampler To Be Used With Charged-Particle X-Ray Fluorescence Analysis, Steven Dee Rowley

Theses and Dissertations

A remote aerosol sampler, capable of up to 3 weeks continuous sampling has been developed. It consists of an Anderson 2000 Inc. mini-sampler or personnel monitor requiring an air flow of 1.4 e/min, a flow meter, a vacuum meter, a bleed valve, a dry gas volume meter, and a pump. The pump is a Brailsford Model TD-4X2, and operates on a 24 volt D.C. power supply. The sampler consists of four impaction stages with a 0.4 μ Nuclepore backup filter. Particulates are removed from the plates in an ultrasonic cleaner with hexane solvent. The suspended particulates are collected on a …

The Effect Of Sheet Moisture On The Anisotropy Of Paper Subjected To Various Degrees Of Restraint During Drying, Ivan T. Mascarenhas

Masters Theses

No abstract provided.

Effect Of Sodium Ions On The Electrochemical Reduction Of Diethyl Fumarate In Dimethylsulfoxide And Acetonitrile, Michael D. Ryan, Dennis H. Evans

Chemistry Faculty Research and Publications

No abstract provided.