Physical Sciences and Mathematics Commons^™

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

The Analysis Of N-Methylscopolamine Bromide By High Speed Ion Pair Partition Chromatography, John L. Nappier

Masters Theses

No abstract provided.

The Response Of The Micro-Adsorption Detector To Inorganic Anions, Maria E. Munera

Masters Theses

No abstract provided.

A Study Of The Acid Etch Pretreatment Used With The Nuva-Seal" Dental Process, Judith Ann Komoroski

Honors Theses

Nuva-Seal, a bisphenol-A-glycidyl-methacrylate polymer, is applied to the occlusal surface of teeth to prevent tooth decay. Before application of the sealant, the enamel surface is etched for one minute by a 50 percent by weight solution of phosphoric acid containing seven percent by weight of zinc oxide. This treatment renders the tooth surface more porous and surface active to insure a strong bond between tooth and sealant. Past studies at Union College have shown that the etching treatment removes much of the enamel from the tooth. In the current work the amount of tooth removed by acid etching was determined …

The Decomposition Of Azibenzil In The Presence Of Oxygen, Nancy C. Westby

Honors Theses

The ozonolysis of acetylenes is thought to proceed through the formation of ∝-carbonyl carbonyl oxide intermediates. This reaction has been shown to parallel the effect of molecular oxygen on ketocarbenes. Azibenzil, a diazo-ketone, will decompose to a ketocarbene by the action of heat, light or catalyst. The ketocarbene may decompose by two pathways: Wolff rearrangement and non-rearrangement. The Wolff rearrangement route will produce methyldiphenylacetate (upon addition of methanol), benzophenone, tetraphenylglycolide and possibly other high molecular weight polymeric species. The non-rearrangement pathway will presumably produce ∝-carbonyl carbonyl oxides which will decompose under varying circumstances to produce benzyl, benzoic anhydride, benzophenone, tetraphenylglycolide …

The Addition Of Singlet Oxygen To N, N-Diethyl-1-Propynylamine, Kenneth S. Zimmerman

Honors Theses

The addition of singlet oxygen to N, N-diethyl-1-pro-pynylamine produced 60-75% yields of N, N-diethyl pyruvamide and various carbon dioxide contamination products under several conditions. Products under several conditions. Product formation was independent of solvent and photosensitizer and was shown to proceed via a singlet oxygen addition mechanism with no free radical involvement. The water addition product was also demonstrated to be N, N-diethyl propanamide. A dioxetene intermediate is suggested as the precursor of N, N-diethyl pyruvamide.

The Preparation And Kinetics Of A Sterically Hindered Gold (Iii) Complex, Michael R. Golden

Honors Theses

The alkyl substituted gold (III) complex [Au(1, 4, 7-Me3dien)Cl] (PF6)2 [where 1, 4, 7-Me3dien respresents (CH3) HNCH2CH2N(CH3)CH2CH2NH(CH3)] has been synthesized. The cation of this compound differs from previously synthesized gold (III) complexes of similar structure since it can form a conjugate base only by loss of hydrogen from a terminal nitrogen. Aqueous solution chemistry studies of this ion reveals that the Cl- is hydrolyzed before loss of a proton from the ligand which is the reverse of the sequence observed with previously studied ions. Monobromo substitution rates are found to be slower than for the complex with no alkyl substitution …

Reactions Of Diazoketones With Neighboring Carbon-To-Carbon Double Bonds, Robert James Perry

Honors Theses

It was hoped that the carbon-carbon double bond in an unsaturated diazoketone would act as a nucleophile in an intramolecular attack to give a ring closure. Experimental results indicate that the double bond did participate, but in such a manner so as to give only substituted products, rather than cyclic ones. We suggest a diazonium salt intermediate in the initial formation of these substituted products. Polymerization and oxonium formation after reactopm with a Lewis acid solvent account for the polymers formed and some of the substituted products.

Co2 Laser Induced Decomposition Of Freon 113, Richard S. Herrick

Honors Theses

Irradiations were made on CCl2FCClF2, Freon 113, to see if the resulting decomposition was photochemical in nature. The irradiation source was Molectron 250, continuous wave, infrared laser operating in the single line mode. The wavelength of irradiation was varied over the range 9.473 µ to 9.734 µ. The pressure except one (in which the cell window broke). Relative rates of reaction were calculated for a constant power absorbed by the sample of 7.8 ± 4W. These relative rates were plotted against the irradiation wavelength. This was superimposed on a plot of the IR band for Freon 113 which was irradiated …

Crown Ethers : Applications In Inorganic Synthesis, Robert L. Sundberg

Senior Scholar Papers

The ability of macroheterocyclic compounds to complex with ionic species has led to the synthesis and investigation of many multidentate macroheterocyclic species. The most stable complexes are formed between macrocyclic polyetheral ligands (crown ethers) with alkali or alkaline earth metal iona. There is an excellent correlation of the stability of these complexes with the size of the cation and the site of the cavity in the macrocyclic ligand. Additional factors, such as the basicity of the ligand and the solvating ability of the solvent, also play important roles in the stabilization of the complex. The stability of such complexes has …

The Investigation Of 3,4- Dipheny1-3- Cyclobutene-1, 2-Dione As A Precursor To A Bis-Ketene, John Dana Myers

Master's Theses

The purpose of this research is to investigate the use of 3, 4-diphenyl-3-cyclobutene-1, 2-dione as a synthetic precursor to bis-ketenes and ultimately examine the chemical behavior of this relatively unknown system. We intend to investigate some of the chemical behavior of bis-phenylketene produced by the well-documented photochemical ring opening of 3, 4-diphenyl-3-cyclobutene-1, 2-dione. Specifically the use of alkenes a chemical traps for the bis-ketene will be investigated. These reactions will be compared and contrasted to the behavior of the ketenes and vinyl ketenes.

Coordination Chemistry Of Bidentate Difluorophosphines, Darrell Lynn Gallup

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The reactions of 1, 2–bis(difluorophosphino)cyclohexane, PF₂C₆H₁₀PF₂, with hexacarbonyls of Cr(O), Mo(O), and W(O) have been extensively investigated. The hexacarbonyls react, either under photolytic or thermolytic conditions, to produce carbon monoxide and oily mixtures of products of the general formulations, [M(CO)₄(PF₂C₆H₁₀PF₂C)]_x, where x varies apparently from 1 – 4. The higher values of x, corresponding to species involving bridging ligands, are more common to the photolysis rather than the thermolysis reactions. Photolysis reactions of Mo(Co)₆ with increasing amounts of the …

Studies Toward The Synthesis Of A- And B- Mercapto Alanine Derivatives, And Of A,B- And B, B- Dimercapto Alanine Derivatives, Aldean James Kolar

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

A convenient, economical, large scale synthesis of N-acetyldehydro-alanine (a-acetamidoacrylic acid) and its methyl ester was developed via a sequence of N-chlorination-dehydrochlorination. The method was extended to the synthesis of the corresponding N-benzoyl, N-phenylacetyl and N-benzyloxycarbonyl derivatives.

The conversion of a-methoxy-N-acetyl alanine derivatives to the corresponding a-mercapto alanine derivatives, using zinc chloride and an appropriate mercaptan, was investigated. Methyl a-methoxy-N-acetyl-D, L-alaninate was successfully converted to the a-acetylthio derivative, in 24% yield; however, a 90% yield could be obtained by treatment of the dehydroalanine derivative with hydrogen chloride gas in neat thiolacetic acid.

A facile conversion of the a-acetylthio derivative to the …

Comparative Enzymology Of Glyoxalase I, Christina Margaret Schimandle

Chemistry and Chemical Biology ETDs

The role of the metal ion in rat erythrocyte glyoxalase I was evaluated. The apoenzyme was formed by dialysis against an EDTA-imidazole buffer. Fluorescence studies of the Mg⁺⁺- and Mn⁺⁺-dansylated glyoxalase I's suggest that the metal ion is near the active site of the enzyme and participates in the catalytic reaction. Stereochemical studies of the conversion of methylglyoxal to S-lactoylglutathione with Mg⁺⁺, Mn⁺⁺, Co⁺⁺ and Ni⁺⁺-glyoxalase I's show that the 0-lactate of S-lactoylglutathione (97±1.5%) is formed. This result suggests that the reaction mechanism is the same with a change …

The Synthesis And Characterization Of Several Copper (Ii) Complexes Of Quinuclidinone-Containing Ligands. Possible Models For Type I Copper Blue Proteins., Victor Thomas Wilcox

Masters Theses

Several copper (II) complexes with bidentate quinuclidinone containing ligands have been synthesized and characterized. These complexes appear to be possible models for the type I copper (II) in the copper "blue" proteins. The spectral and magnetic properties indicate that the complexes have a pseudo tetrahedral microsymrnetry about the central metal ion. The complexes contain chromophores of the following forms: CuN₄, CuN₂O₂, and CuN₂x₂, where X is either Cl or Br. While the spectra of these complexes lack the intense 17,000 cm^-1 band typical of copper "blue" proteins, the optical …

Nucleophilic Substitution At Phosphorus In Six-Membered Ring Phosphate Esters, Mike Bauman

Electronic Theses and Dissertations

From these results the following conclusions may be drawn: 1. The stereochemistry of nucleophilic substitution at phosphorus is influenced by the basicity of the leaving group with the more basic leaving group favoring retention. 2. Lithium ion diverts the reaction to retention by forming an intimate ion-pair with the nucleophile which then attacks phosphorus. This associated ion is less reactive than the unassociated nucleophile. 3. For the retention mechanism the leaving group participates in the rate determining step. 4. The mechanism for retention entails a more sterically unfavorable configuration than for inversion.

Specificity Of Antisera Against Hordeum Vulgare Ribonuclease And Serological Quantitation Of The Enzyme In Tissue Extracts, Steven Bryan Hawthorne

Electronic Theses and Dissertations

Specific rabbit antisera against purified seedling RNase I from both a hardy (Dicktoo) and less-hardy (Tennessee Winter) cultivar of winter barley was obtained using a 1 mg injection schedule. Both antisera formed a single precipitin band on double immunodiffusion and immunoelectrophoresis when reacted with the homologous crude tissue extract. RNase antigen from either cultivar was highly cross-reactive with both antisera. Passive hemagglutination inhibition was used in an attempt to distinguish purified RNase from both cultivars. A consistent difference in anti-RNase serum specificity between cultivars was shown, but the difference observed by this method was not sufficient to conclude structural differences …

Studies On The Gas Given Off By Yeast When It Goes From An Anaerobic To Aerobic Metabolism, David C. Potts

Electronic Theses and Dissertations

Several investigators have observed that when yeast cells (yeast) go from a strictly anaerobic environment to an aerobic oner and glucose is added a negative value is recorded on the manometer. This phenomenon indicates that a gas has been given off by the yeast. The purpose of this research was to identify the gas and determine how it arises.

Synthesis And Resolution Of Enantiomeric Quaternary Ammonium Halides, Wei Lee

University of the Pacific Theses and Dissertations

The purpose of the work described in this thesis was the synthesis of a new class of surfactants containing chiral cationic end groups and the synthesis of two chiral reactant molecules which would react in the presence of these surfactants. The structures of the surfactant and substrate molecules were designed to maximize their stereochemical interactions and in this way reveal details of the nature of micellar catalysis. In order to indicate why these structures were selected, several examples of micellar catalysis and the factors influencing it will be discussed in the following pages.

Direct Determination Of Pentachlorophenol By Differential Pulse Polarography, Albert L. Wade

Theses and Dissertations

Concern over environmental contamination leading to the introduction of pentachlorophenol into human and animal systems has resulted in the need for a rapid and direct method for determining trace concentrations of this highly toxic compound. A direct electrochemical procedure has been developed for determining trace conccentrations of this phenol dovm to 0.27 ppm. This method uses the electrochemical techniques of differential pulse polarography at the dropping mercury electrode, and differential pulse voltammetry at the carbon paste electrode to reduce pentachlorophenol for this determination. Cyclic voltammetry at the hanging mercury drop electrode has been used to characterize the reaction behavior of …

Reduction Of 1,2 Cyclopentanedione With Lithium Aluminum Hydride, David Curtis Winn

Dissertations, Theses, and Masters Projects

No abstract provided.

New Evidence Supporting The Assignment Of Glutamic Acid As An Iron Ligand In Hemerythrin, Patricia M. Gormley

Dissertations and Theses

The amino acid sequence determination of Phascolopsis gouldii hemerythrin in the region of the proposed iron ligand at position 58 was the main objective of this research endeavor. Generation of a large peptide was pursued by trypsin digestion of citraconylated hemerythrin producing peptide 50-113 for sequenator analysis. Detection of the phenylthiohydantoin amino acid derivatives by gas-liquid and high-performance-liquid chromatography yielded unambiguous sequence elucidation through the region of interest identifying residue 58 as glutamic acid.

Molybdenum(V) Solutions In Hydrobromic Acid, Edwin Charles Perley

Electronic Theses and Dissertations

Interest in the coordination chemistry of molybdenum has increased greatly in recent years because of the discovery that molybdenum plays an active role in several redox enzymes. Model systems have been devised to gain insight into the function of molybdenum in these enzymes. Most model systems are believed to contain an oxomolybdate(V) dimer in equilibrium with a redox active monomer or dimer. A relatively simple system that shows important similarities to model systems is a molybdenum(V) solution in hydrobromic or hydrochloric acid. As in the model systems, these solutions are believed to contain monomers and dimers in equilibrium. The equilibria …

Purification And Characterization Of Nadh Oxidase And Peroxidase From Lactobacillus Casei, Louise Ann Barstad

Dissertations and Theses

A protein exhibiting NADH oxidase and NADH peroxidase activity has been isolated from Lactobacillus casei in high purity. Evidence obtained through gel filtration, electrophoresis, and electrofocusing indicates that the two activities are characteristic of a single tetrameric protein with an approximate molecular weight of 240,000.

An Investigation Of Arsenic(V)-Catechol Complexes, Ronald P. Haak

Dissertations and Theses

There is not, at this time, a simple method for the simultaneous determination of As (III) and As (V) at trace levels. The development of such as method is needed, as the toxicities of these two species differ so greatly.

As (III) and As (V) are polarographically reducible in the presence of excess catechol, but the wave produced by As (V) is depended on time, pH and catechol concentration as well as As (V) concentration. In order to understand this behavior, determination of formation constants for any complex species present were needed to identify which species is electroactive. The literature …

Mechanism Of Phenyl Azide-1,2-Cyclonoadiene Adduct Formation And Isomerization Of This Adduct, Isom Harrison

University of the Pacific Theses and Dissertations

A major purpose of this research was to investigate the mechanism of aryl azide addition to allenes. Much evidence has accumulated in support of a concerted mechanism for aryl azide additions to simple alkenes. Consistent with these findings, this addition is a symmetry allowed process. The analagous aryl azide additions to allenes have received little mechanistic study. The approach taken in this work was to probe the mechanism by using optically active 1,2-cyclonanadiene, observing the stereochemistry of the adduct formed upon addition of phenyl azide.

Another goal was to investigate the isomerization of the phenyl azide-1,2-cylononadiene adduct, 10-phenyl-10,11,12-triaza-△ 11 -bicyclo …

Synthesis And Flame Retardant Studies Of Bromoester Of 2,4-Pentadienoic Acid, Hessam Ghane

Retrospective Theses and Dissertations

The synthesis and fire retardancy of several bromoesters of 2,4-pentadienoic acid were investigated. The synthesis of 2,4-pentadienoic acid was accomplished by liquid phase reaction of acrolein and malonic acid in the presence of pyridine. The conversion of the acid to bromoesters was performed by two different procedures. In the first procedure, the corresponding acid chloride was prepared from the acid via reaction with SOCl2 in the presence of powdered (3A°) molecular sieves. The molecular sieves serve as an internal trap for by-product HC1 and inhibit the competing polymerization reaction of the acid chloride. Reaction of the acid chloride with various …

The Vapor Phase Oxidation Of 1, 3-Pentadiene, David E. Sasser

Retrospective Theses and Dissertations

The vapor phase oxidation of 1.3-pentadiene, over heterogeneous catalysts, was investigated with the objective of producing 2,4-pentadienal and 2,4-pentadienoic acid. Copper and cobalt-molybdenum catalysts, both supported and unsupported, were utilized at various reaction temperatures, residence times and feed ratios. The matter of 1,3-pentadiene vaporization and introduction into the reactor system proved to be critical. Low temperature vaporization of the hydrocarbon and dilution with the oxidant, air, was found to be necessary to avoid polymerization of the feed. Alumina-supported catalysts were found to be very active, leading to severe cracking of the hydrocarbon feed and subsequent carbonization of the catalysts. Silica-supported …