Physical Sciences and Mathematics Commons^™

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 …

Second Row Molecular Orbital Calculations. Geometries, Internal Rotation Barriers, And Dipole Moments Of Methylsilane, Disilane, Methyl Mercaptan, And Methyl Phosphine, Mark S. Gordon, Loren Neubauer

Mark S. Gordon

The internal rotation barriers of methylsilane, methyl mercaptan, methylphosphine, and disilane are calculated with and without complete geometry optimization in three different CNDO parametrizations. It is found that Santry's recent reparametrization is most reliable for both geometries and barriers and that geminal and bonded interference interactions are more important than those between vicinal atoms for these molecules. None of the parametrizations give reasonable dipole moments.

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 …

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 …

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.

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 …

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. …

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.

Effect Of Molecular Angular Momentum On The Thermal Conductivity Of A Multicomponent Gas Mixture, Louis Biolsi Jr., Edward Allen Mason

Chemistry Faculty Research & Creative Works

The effects of molecular angular momentum (spin polarization) on the thermal conductivity of a multicomponent gas mixture are considered. The Wang Chang-Uhlenbeck approach to the kinetic theory of gases with internal states is used. Formal results are obtained for the thermal conductivity of a gas mixture of uniform composition. These results are given in terms of the quantum mechanical degeneracy-averaged cross section.

The Synthesis And Characterization Of The 2,2'-Bisacylazide Of 2,2'-Diphenyldicarboxylic Acid, Subrata Chatterjee

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this investigation w2s the photolytic and thermal characterization of a newly synthesized aromatic diacylazide, the 2,2'-bisacylazide~ of 2,2'-diphenyldicarboxylic acid 19. Photolysis of the azide in acetone ~ave rise to a mixture of photoproducts, one of which is a known system, 6(5-H)-phenanthridionone 28, while photolysis of 19 in ethanol gave ris,2 to the corresponding hydroxamic acid ester 40.

The Role Of A Dolichol-Oligosaccharide As An Intermediate In Glycoprotein Biosynthesis, An-Fei Hsu, John W. Baynes, Edward C. Heath

Faculty Publications

Incubation of mouse myeloma microsomes with GDP-[(14)C]mannose results in the biosynthesis of [(14)C]mannose phosphoryl dolichol [Baynes, J. W., Hsu, A.-F. & Heath, E. C. (1973) J. Biol. Chem. 248, 5693-5704] and a [(14)C]mannose- and N-acetylglucosamine (GlcNAc)-containing oligosaccharide derivative of dolichol. Thus, [(14)C]mannose phosphoryl dolichol and [(14)C]mannose-labeled oligosaccharide pyrophosphoryl dolichol were isolated from incubation mixtures by solubilization in 2% (w/v) Triton X-100 and the lipids were separated from small molecules by gel filtration fractionation. After removal of radioactive protein from the preparation, the two lipid derivatives were separated quantitatively by fractionation on a concanavalin A-Sepharose column; [(14)C]mannose phosphoryl dolichol was not …

Spectral Studies Of Esters Of 9 And 1 Anthroic Acid, Robert Fisch

Honors Theses

A comparison was made between spectral properties of several atomatic esters of 9- anthroic acid (9- COOAR) and the methyl ester (9-COOMe). The spectral properties observed were absorption spectra, fluorescence quantum yields (Øf) and Stokes shifts. Although all of the ester absorption spectra showed anthracene-like structure, the aromatic ester spectra were clearly more diffuse than the 9-COOMe spectrum. Certain electron delocalization pathways are available to 9-COOAR but not to 9-COOMe, thereby allowing greater carboxyl group-ring interaction for 9-COOAR, resulting in increased spectral diffuseness relative to 9-COOMe. Data are presented which show that the electronic absorption spectra of these esters are …

The Reconversion Of Ethylene Thioketals To Ketones, Jeffrey Paul Ginther

Honors Theses

Many aldehydes, ketones and other carbonyl-containing compounds react with 1, 2-ethanedithol to give highly stable cyclic thioacetals or thioketals. The problem lies in recovering the substituted 1, 3-dithiolanes to the carbonyl compound without altering the other substituents of the molecule. We propose a new direct method of exchange with formaldehyde to reconvert the 1, 3-dithiolane to the carbonyl compound. This was accomplished with 2, 2-diethyl-l, 3-dithiolane. Also, a mechanism is proposed involving the formation of a sulfonium ion intermediate. In preparation for the exchange study seven 1, 3-dithiolanes were synthesized.

A Comparison Of The Spectral Properties Of Anthracene-9-Carboxylic Acid And Anthracene-9,10-Carboxylic Acid, Gail Wendy Goodman

Honors Theses

Previous studies have shown that substitution of a single carboxyl group on the anthracene ring produces fluorescent quantum yields (Øf) and Stokes shifts that are highly solvent dependent. The effects of solvents on the spectral properties of anthracene-9, 10-dicarboxylic acid (9, 10-(COOH) 2) which has symmetrically distributed carboxyl groups, was studied. Comparison is made with spectral data for 9-methyl anthroate (9-C00Me) and anthracene-9, 10-dicarboxylic acid (9, 10-(COOH) 2) which has symmetrically distributed carboxyl groups, was studied. Comparison is made with spectral data for 9-methyl anthroate (9-COOMe) and anthracene-9-carboxylix acid (9-COOH). The absorption and fluorescence spectra of the unprotonated forms of …

Poly (4-Vinylpyridine) Synthesis And Solution Properties, Warren L. Robinson Jr.

Chemistry Honors Papers

This 28 page thesis reports the synthesis of poly (4-vinylpyridine) by cationic and free radical initiators, concentrated sulfuric acid and benzoylperoxide, respectively. The molecular weights of the various samples were measured and an evaluation of the several methods given. The effects of ionic strength and pH on the viscosity of solutions of poly (4-vinylpyridine) were also investigated.

Oxygen Consumption By Acrylamide Polymerization For Rapid Screening Of Chemotherapeutic Agents, Richard A. Johnson '74

Fenwick Scholar Program

This paper describes a screening process used to determine the overall effect of anti-cancer drugs on a tumor more rapidly than other established methods. This technique measures the rate of oxygen consumption by cells when a solution of acrylamide and bisacrylamide is polymerized.

Investigation Of The Mechanism Of Poly (Vinyl Alcohol)-Iodine Complex, David J. Martella

Chemistry Honors Papers

This 24 page thesis examines the PVA-iodine reaction mechanism.

Radiation Effect On Poly-Α-Methylstyrene, Magdi F Iskandar

Archived Theses and Dissertations

No abstract provided.

Photochemistry Of Beta-Methyl-Beta-Nitrostyrene, Peggy Chen

Masters Theses & Specialist Projects

It has been postulated that acetone is the best solvent for the photochemical rearrangement of β-methy1-β-nitrostyrene to 1-phenyl-1, 2-propanedione-1-oxime and it has been postulated to be a sensitizer for this rearrangement. It has also been suggested that the methyl group on the beta-carbon is required for the proper orientation of the nitro group for rearrangement. The irradiation of β-methyl-β-nitrostyrene in several solvents has been studied and the yield of oxime has been recorded. It has been found that several solvents gave yields of oxime higher than that recorded for acetone. We do not, therefore, believe acetone to be necessary to …

Chronopotentiometric And Chronoamperometric Investigations Of Uranium (Vi) In Molten Condensed Phosphates., John J. Miglio

Chemistry and Chemical Biology ETDs

The diffusion coefficient, D, of U (VI) in molten sodium metaphosphate at 694° C was determined by two independent methods. D was also determined at R values of 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5, where R is the molar M₂0 to P₂O₅ ratio and M is univalent. The relative amounts of various phosphate species present in the molten state were determined by thin layer chromatography after rapidly cooling the melt and dissolving the resultant glass in water. With the above information it was hoped to determine if D is inde­pendent of the experimental method …

Conference Keynote Address, John B. Rigg

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

No abstract provided.

Prospects For Conversion Of Solar Energy Into Electrical Power, William R. Cherry

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

In 1972, the Solar Energy Panel took a broad look at solar energy across the whole field to see just what could be done with this energy source. Maybe the era of acquiring energy without regard to cost and without regard to consequences of using it is beginning to come to a close and maybe we ought to start looking at the newer sources of energy, even though we need every bit of energy we can get from every source. I am not trying to say we don't need gas, oil, coal and nuclear energy. We are not going to …

The U. S. Wind Power Program, Joseph M. Savino

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

Today I would like to talk about wind energy in, basically, two parts. I would like to bring to your attention some of the developments that have occurred in the 20th century. Many of us who have gone through school in the last 25-30 years don't recall anywhere in our engineering education much information dealing with wind energy, and that may come as a surprise to you as it did to me, to learn how much has actually been done in the 20th century to develop large scale wind-driven machines. After I get through with that introduction I would like …

Alternate Energy Removal Modes For Nuclear Power Reactors, Robert L. Carter

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

Attention is focussed upon the unique qualities of high energy fission particles, and upon the fundamental limits to the direct removal of their kinetic energy by electrostatic means and by cyclotron resonance deceleration. Efficiencies of secondary and tertiary product ionization and excitation produced by fission particles are examined. The potential for delivery of power through various non-thermal modes is discussed, and the significant unknowns relating thereto are identified.

Locating Nuclear Power Plants Underground, Frank M. Scott

UMR-MEC Conference on Energy / UMR-DNR Conference on Energy

This paper reviews some of the questions that have been asked by experts and others as to why nuclear power plants are not located or placed underground. While the safeguards and present designs make such installations unnecessary, there are some definite advantages that warrant the additional cost involved. First of all, such an arrangement does satisfy the psychological concern of a number of people and, in so doing, might gain the acceptance of the public so that such plants could be constructed in urban areas of load centers. The results of these studies are presented and some of the requirements …