Physical Sciences and Mathematics Commons^™

Chemistry Of Chromium Oxyfluorides And Group Vib Perfluoroglutarates, Bruce Michael Johnson

Dissertations and Theses

Pure chromium oxide trifluoride was prepared for the first time by reaction of CrO₃ and ClF with subsequent multiple fluorine treatments at 120°C. On the basis of its infrared spectrum, the purple CrOF₃ was assigned as a fluorine-bridged polymer with terminal oxygen groups. Chromium oxide trifluoride was found to be stable to 300°C, where it decomposes with the loss of oxygen to CrF₃.

Synthesis And Evaluation Of Polymer Supported Homogenous Oxidation Catalysts, Raymond J. Riley

Retrospective Theses and Dissertations

Polystyrene bis(salicylaldehyde)-propylene-1,3-diiminato Cobalt (II) [salen] and Polystyrene bis(2,4-pentanedione)-propylene-1,3-diiminato Cobalt (II) [BAE] were prepared stepwise from chloromethylated polystyrene. In addition, a new preparation of a Schiff base was attempted resulting in Polystyrene bis(salicylaldehyde)-isobutylene-1,3-diiminoato Cobalt (II) being produced. Optimum reaction conditions were determined with regard tot ime, temperature, reaction ratios and solvent for each step for the reaction. The ability of the above named Cobalt (II) Schiff bases to oxidize 3-methyl indole to give the corresponding o-formylaminoacetophenone was also studied. One polymer-bound Schiff base cobalt catalyst (co-salen) demonstrated a very small amount of catalytic activity resulting in a minimum amount of o-formylaminoacetophenone …

Synthesis Of Dihydroisoquinolines And Tetrahydroisoquinolines, John J. Schlager

Chemistry & Biochemistry Theses & Dissertations

Dihydroisoquinolines and tetrahydroisoquinolines are compounds which possess a variety of pharmacological activities. New easier methods of synthetic manipulations of these structures is of constant interest in the pharmaceutical industry.

This paper describes a new three step method of preparing 1-alkyl- and 1-aryl-tetrahydroisoquinolines from a tetrahydroisoquinoline. The synthesis involves the N-chlorination of tetrahydroisoquinoline followed by dehydrohalogenation with potassium superoxide. The reaction products are the dihydroisoquinolines. Overall yields range from 85-96%. The unsubstituted, 1-methyl-, and 1-phenyl-J,4-dihydroisoquinolines have been formed. Organometallation of the unsubstituted dihydroisoquinoline provides the 1-substituted tetrahydroisoquinoline. The 1-benzyl-, 1-n-butyl-, 1-ethyl-, 1-methyl-, and 1-phenyl-1,2,J,4-tetrahydroisoquinolines were prepared. The use of Grignard and …

Some Physical And Mechanical Properties Of Iron Calcium Silicate Glasses-Iron Composites, Hani Louis Rizkalla

Archived Theses and Dissertations

No abstract provided.

Reactions Of (3-(Dimethylamino)-2-Azaprop-2-En-1-Ylidene) Dimethylammonium Chloride (Gold's Reagent) With Carboxylic Acid Derivatives And Grignard Reagents, Dale E. Polk

Retrospective Theses and Dissertations

An azavinamidium salt, [3-(Dimethylamino)-2-azaprop-2-en-l-ylidene] dimethylammonium chloride was reacted with primary amides, esters containing an ╬▒-methylene group and Grignard reagents. The reaction of this azavinamidium salt with amides and esters produced respectively, acyl amidines and enamino esters. Both of these products were produced in high yields by using relatively mild conditions. Reaction of the salt with Grignard reagents resulted in a novel synthesis of aldehydes. This aldehyde synthesis was shown to be of general utility and to proceed in high yields.

Electrochemical And Spectroscopic Studies Of Some Less Stable Oxidation States Of Selected Lanthanide And Actinide Elements, David Edward Hobart

Doctoral Dissertations

The technique of simultaneous observation of electrochemical and spectroscopic properties (spectroelectrochemistry) at optically transparent electrodes (OTE's) has been applied to the generation and characterization of some less stable oxidation states of selected lanthanide and actinide elements (Ce, Pr, Sm, Eu, Tb, Yb, U, Np, Am, and Cm) in complexing and noncomplexing aqueous solutions. Optically transparent electrodes used in this study included reticulated vitreous carbon (RVC) and metal screen OTE's and a new OTE made from porous metal foam (PMF).

Cyclic voltammetry at microelectrodes was used in conjunction with spectroelectrochemistry for the study of oxidation-reduction (redox) couples. In some cases additional …

A Spectrophotometric Study Of The Rate Of Formation Of Violet Peroxychromate In Aqueous Solution, Stephen N. Witt

Honors Theses

The rate of formation of violet peroxychromate in aqueous solution was monitored spectrophotometrically at 540 nm. The method of initial rates enabled us to determine the exponents, x, y, and z, in the rate law for the violet species.

A Survey Of Detection Methods For Ovulation And A Proposed Method For Estrogen Determination, Maria Lanni

Honors Theses

A rapid, accurate method of determining the exact phase of a menstrual cycle at a given time is extremely important. This information is vital to doctors studying menstrual abnormalities and more importantly as an aid in conceptive and contraceptive decisions. Many methods based on changes in the body have been used to detect ovulation. These nonquantitative methods depend on the cyclical variations in basal boy temperature, physical and chemical properties of mucus and content of saliva. These changes are influenced by changing hormone levels. Specicially, estrogen levels rise several days prior to ovulation, therefore, methods for determining estrogen concentration in …

Synthesis Of Carbon Nucleosides : Potential Antibiotics, Jeffery Davis

Senior Scholar Papers

Abstract This paper deals with two synthetic routes designed to yield carbon nucleosides. The C-nucleosides are compounds of potential antibiotic utility. The first approach, designed to yield 4-(2'-deoxyribofuranosyl )-1 ,2,3-triazole (1), consisted of silylation of methyl vinyl ketone (4) to give 2-trimethylsilylosy-l,3-butadiene (6), followed by a crossed aldol condensation with a heteroaromatic aldehyde to yield the aldol l. Epoxidation and cyclization of l was expected to yield the target molecule ~. The initial step, silylation of methyl vinyl ketone (4), was successful. Using model compounds the second step of the synthesis was attempted. Numerous attempts to condense (6) with 2-pyridinecarboxaldehyde …

Mechanism Of Two Homogeneous Reactions; Co Self Exchange And N2 Self Exchange, Alan L. Rockwood

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The two atom switching reactions referred to in the title were originally studied at temperatures greater than 2000°K in shock tubes by other investigators. For each reaction they proposed a direct four-center exchange mechanism in which one of the reactant molecules must be vibrationally excited, (the vibrational excitation mechanism or VEM). One of the predictions of the VEM is that molecules which are vibrationally hot but translationally cold should react through the four center transition state that leads to exchange.

Using a mercury photosensitization technique, it is shown in the present work that excitation of CO to high vibrational levels …

The Transport And Intracellular Distribution Of Iron In The Basidiomycete, Ustilago Sphaerogena, Charles W. Passavant

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The transport and intracellular distribution of iron in Ustilago sphaerogena via the native siderochrome ferrichrome A has been examined. Evidence is presented which suggests the involvement of deferriferrichrome in iron transport when the metal is supplied to the cell as ferrichrome A. This process requires both oxygen and ATP synthesis and may require a transmembrane electrochemical gradient. Once inside the cell, iron derived from ferrichrome A is rapidly distributed, with a major fraction found in the mitochondria, presumably as heme.

The kinetics of ferrichrome and ferrichrome A uptake have also been investigated. The Km of transport of ferrichrome was …

Comparison Of Toxicological Models For Evaluation Of Air Pollutants: Response Of The Pulmonary Alveolar Macrophage To Hexavalent Chromium, Jennifer Baker Galvin

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

This study was designed to accomplish two primary objectives: (1) to compare two test methods commonly used to evaluate toxicity of inhaled air pollutants, and (2) to observe the response as measured by each of the methods, of pulmonary alveolar macrophages exposed to 2μg hexavalent chromium.

The first method evaluated featured use of intratracheal injections to simulate live inhalation exposures, and the second required exposure of macrophages cultured on petri plates. Pulmonary alveolar macrophages harvested from Long Evans rats were used. The two cell function parameters measured in the evaluations were chemiluminescence and oxygen consumption (which was determined for cells …

Chemistry Of Organic N-Chloramines, Formation Of Arenesulfonamides By Derivatization Of Organic N-Chloramine With Sodium Arenesulfinate, Katherine F. Bowdring

Chemistry & Biochemistry Theses & Dissertations

Organic N-chloramines are recognized by-products of chlorinated water systems. Because of their chemistry, none have been isolated or identified.

This paper discusses a method for the derivatization of the organic N-chloramines based on a nucleophillic substitution mechanism. N-Chloro derivatives of amines of various structures were studied including primary and secondary aliphatic amines, as well as amino acids. The effect of the presence of other functional groups including aromatic and unsaturated systems was investigated.

Derivatization was done by three different methods, one involving derivatization of the pure N-chloramine, and two involving derivatizations of the N-chloramine generated in situ. Seventeen arenesulfonamides have …

High Performance Liquid Chromatographic Analysis Of Biogenic Amines, Thais Edwina Ahrendt Keegan

Chemistry & Biochemistry Theses & Dissertations

The objectives of this research were to develop a sensitive method for separation and quantitation of biogenic amines and to apply that procedure by monitoring neurochemical changes resulting from stimuli to the test system.

Primary aromatic amines were derivatized with o-phthalaldehyde-mercaptoethanol prior to chromatography, Separation of the fluorescent adduct was achieved using a μBondapak/ phenyl reversed-phase column and a two-step gradient of methanol:0.08 M acetic acid, pH J.O. Fluorescence was monitored using a J40 nm excitation energy and an emission filter which transmits radiation greater than 400 nm (50% T at 418 nanometers).

Following optimization of the chromatographic conditions, studies …

A Technique For The Isolation And Identification Of Aliphatic Amines In Water, Peter Alan Drew

Chemistry & Biochemistry Theses & Dissertations

Small, aliphatic amines added to a basic, aqueous solution (16.2 L) at a concentration of 100 parts per billion were isolated by sorption on a small column of macroreticular resin. The amines were eluted with diethyl ether; the eluate concentrated, and the compounds separated and identified by gas chromatography. The efficiency of the recovery of a-nines ranged from 5 to 28%.

A protocol for derivatizing pyrrolidine and n-pentylamine in ether with fluorinated acylating agents was developed. The method was found to be adequate for the detection of approximately 13 micrograms of &-nines in concentrated ether extract.

Environmental water samples …

Determination Of Diffusion Coefficients Of Ions In Gels, Kelly A. Sanderson

Theses & Honors Papers

No abstract provided.

A Matrix Isolation Study Of The Reactions Of Oxygen(Singlet-D) With The Chlorofluoromethanes Fluorotrichloromethane, Dichlorodifluoromethane And Chlorotrifluoromethane, Richard Thomason Burke

University of the Pacific Theses and Dissertations

We have studied the reactions of O(¹D) with CC1₃F, CC1₂F₂ and CC1F₃ in CO₂, SF₆ and N₂O matrices, and in neat mixtures. Photolysis of cryogenic mixtures of ozone and the chlorofluoromethanes in various matrix hosts resulted in production of O(¹D) which migrated through the matrix to react with the Freon molecules. Products were detected by infrared spectroscopy of the matrix deposits, with assignments confirmed by comparison of ¹⁶O and ¹⁸O absorption bands with literature values. Evidence for oxygen atom insertion into a C-C1 …

The Acid-Catalyzed Hydration Of Phenylallene, Gary Wayne Long

Dissertations, Theses, and Masters Projects

No abstract provided.

Controlling The Number Of Metal Sites To Which A Polytertiary Phosphine Coordinates In Tungsten Carbonyls, Rodney D. Borger

Masters Theses

Judiciously selected coordinated fragments of Ph₂PCH₂CH₂PPhCH₂-CH₂PPh₂ [(OC)₅WPPh₂H, (OC)₅WPPh₂CH=CH₂ and (OC)₅WPPh(CH=CH₂)₂] were used to construct its five possible nonchelated pentacarbonyltungsten complexes. These are the trimetallic (OC)₅WPPh[CH₂CH₂PPh₂W(CO)₅]₂ and the two pairs of constitutional isomers, (OC)₅WPPh[CH₂CH₂PPh₂]₂ and (OC)₅WPPh₂CH₂CH₂PPhCH₂CH₂PPh₂, and PPh[CH₂CH_{2 …}

Analysis Of Coal Fractions Using Dibromotriphenyl-Phosphorane: A Selective Ether Cleaving Reagent, Michael L. Ballard

Masters Theses

Dibromotriphenylphosphorane (DTP), in acetonitrile at 40°C, was found to cleave benzyl phenyl ether in preference to di-alkyl or other aryl alkyl ethers. Competition between 10 mmoles benzyl phenyl ether and 10 mmoles di-n-octyl ether for 0.92 mmole of DTP gave 48% cleavage of benzyl phenyl ether and 1.3% cleavage of di-n-octyl ether based on DTP. Reaction of benzyl phenyl ether and di-n-octyl ether separately with DTP at 40°C produced 80% and 8% cleavage, respectively. Reactions of DTP with diphenyl ether, butyl phenyl ether, phenyl cyclohexyl ether and benzyl benzoate at 40°C produced less than 3% cleavage in all cases.

Reaction …

Pyridine Hydrogen Iodide As An Ether Cleaving Agent In Coal Chemistry, Agnes Mei-Ying Chen

Masters Theses

Reactions of several phenyl ethers and an ester with pyridine hydrogen iodide were examined under various conditions as model studies for the recently reported molecular weight reduction of a fraction of Illinois No. 6 coal by hydrogen iodide in pyridine at 50°.

No ether or ester cleavage was observed at 60-80° in pyridine, acetonitrile, ethanol or the absence of solvent. Sealed tube reactions at 210° resulted in cleavage to phenol plus various hydrocarbon and alkyl halide products. Pyridine and benzyl phenyl ether at 210° produced no cleavage in the absence of hydrogen iodide.

Syntheses of crystalline pyridine hydrogen iodide and …

Sodium Accumulation In Serpentine And Non-Serpentine Populations Of The Milkweed Asclepias Fascicularis, Paul N. Thomas

University of the Pacific Theses and Dissertations

Because Asclepias fascicularis is found on both serpentine and non-serpentine soils in California and because it was reported to accumulate sodium, this study was initiated to establish the degree of accumulation of this ion in these two soil types. Two other species, Asclepias speciosa Torr. and Asclepias cordifolia (Benth.) Jeps. were included to determine if this characteristic of accumulation occurs in other members of this genus.

Neutron Activation Analysis Of Nuclides From Stellar And Man-Induced Nuclear Reactions, Lawrence Lee Oliver

Doctoral Dissertations

"Neutron activation and γ-counting were used to determine the relative abundances of six stable tellurium isotopes in the acid-etched residues of the Allende meteorite. The results were correlated with the isotopic compositions of xenon and the elemental abundances of helium and neon in similarly prepared residues. Nucleosynthesis appears to be the only viable explanation for the anomalous isotopic and elemental compositions observed in these residues. Our results suggest that the solar system condensed from an isotopically and chemically zoned nebula that was produced by the explosion of a supernova, concentric with the present sun.

A combination of neutron activation and …

Interpretation Of Gc-Ms Data By Reverse Search And Relative Retention Indices, Christopher Hein

Dissertations, Theses, and Masters Projects

No abstract provided.

Isolation And Characterization Of Frullanolide From Frullania Franciscana (Howe), Marshall Stuart Sass

Dissertations and Theses

Investigation of the ether extract of the liverwort Frullania franciscana (Howe) resulted in the isolation of the sesquiterpene lactone frullanolide. The separation techniques of thin-layer chromatography, dry column chromatography, and liquid column chromatography were evaluated. Only liquid column chromatography was found useful. Fractions from alumina liquid column separations had infrared spectra which resembled the published spectrum of frullanolide. The identity of the compound obtained from F. franciscana (Howe) was established after extensive purification by comparison of its infrared and nuclear magnetic resonance spectra with published spectra of frullanolide.

Cis Labilization: A Study Of The Reactions Of Group 6 Pentacarbonyl Phosphido Anions, Matthew J. Madigan

Masters Theses

The synthesis of cis-(OC)₄M(PPh₂H)L (M=Cr,Mo,W; L=PPh₃,PPh₂Et,PPhEt₂,PEt₃) can be achieved by treating (OC)₅MPPh₂H with potassium tert-butoxide in the presence of L. […] The products are easily isolated and are not contaminated with trans isomers. Obtained as a minor product is [(OC)₄MPPh₂]₂.

The reaction of (OC)₅WPPh₂H with potassium tert-butoxide generates [(OC)₅WPPh₂]^- which reacts with (OC)₅WPPh₂H to give [(OC)₅WPPh₂W(CO)₅] …

Spectroscopic Studies Of Pre-Mixed Hydrocarbon Flame Plasmas, Tsao-Chin C. Huang

Masters Theses

This thesis contains two different studies.

Chapter 1, "Infrared Emission Spectrum of the Hydroxyl Radical.", is in collaboration with Dr. Giles L. Henderson and Mr. Chun-Sheng Ko. This chapter has been submitted and accepted for publication by the Journal of Chemical Education.

In this chapter, we describe a rather novel physical chemistry experiment in which ab initio potential parameters for the OH radical are compared with those obtained from the ir emission spectrum of an oxy-acetylene welding torch.

Chapter 2, "A Preliminary Spectroscopic Study of Field-Induced Ion Movements in Flame Gases.", describes the effects of longitudinal electric fields on CH …