Physical Sciences and Mathematics Commons^™

Orbit Structure Of Finite And Reductive Monoids, Zhuo Li

Digitized Theses

A reductive monoid is an algebraic monoid with a reductive unit group. We introduce a new class of reductive monoids, $({\cal T}, \sigma)$-irreducible monoids. Generally, we have the question of finding the orbits of the unit group of a reductive monoid acting on both sides of the monoid. Putcha and Renner give a recipe to determine the orbits for ${\cal T}$-irreducible monoids. Motivated by their construction of finite reductive monoids, the concept of (${\cal T}, \sigma)$-irreducible monoid arises naturally.

We obtain that the ${\cal T}$-irreducible monoids turn out to be a special class of the $({\cal T}, \sigma)$-irreducible monoids. We …

A Characterization Of Extractable, Hydroxylated Fatty Acid Bearing Components In Legionella Pneumophila, Jonathan R. Lane

Electronic Theses and Dissertations

Extraction of the lipids of Legionella pneumophila yields phases unlike those produced from other Gram-negative bacteria. A viscous interface forms between the aqueous (wash) and organic phases. More than half of the hydroxylated fatty acids were found distributed between the aqueous phase and the interfacial material, fractions in which such constituents have not been reported in other Gram-negative species. It was further observed that after the material from the aqueous/interfacial phase was dissolved in methanol or chloroform/methanol (2:1 (V/V)), the addition of acetone would create a white, flocculent precipitate. Analyses showed that the supernatant contained fatty acids that were nonhydroxylated …

The Effect Of Tungsten(0)Pentacarbonyl On Coordinated Ligands, Janice Imada Byington

University of the Pacific Theses and Dissertations

A series of monosubstituted tungsten(0)pentacarbonyl complexes, W(CO)₅L (L = water, hydrogen sulfide, pyrazine, pyrimidine, 4,4'-bipyridine, 4-cyanopyridine, isonicotinamide, and methanol) were synthesized and characterized. The purpose of this project was to determine the effect of the W(CO)₅ moiety on the coordinated ligand, L.

The visible spectra of the synthesized W(CO)₅L complexes typically exhibited a maximum around 400 nm ((epsilon) (TURN) 4000). The infrared spectra of these complexes exhibited the characteristic three band pattern (2A₁ + E) in the carbonyl region ((TURN)2070 cm^-1, (TURN)1930 cm^-1, (TURN)1900 cm^-1. The pKa's of …

S-Adenosyl- L-Methionine And S-Adenosyl- L-Homocysteine: A Nuclear Magnetic Resonance Study And Purification Of S-Adenosyl- L-Methionine: L-Homocysteine S-Methyltransferase From Saccharomyces Cerevisiae, Mark Lewis Stolowitz

University of the Pacific Theses and Dissertations

An analysis of the 360 MHz ('1)H NMR spectra of the title compounds in ('2)H(,2O) is presented. The ('3)J values for the ribose vicinal protons of S-adenosyl-L-methionine are consistent with a predominantly C(,3')-exo conformation and with one highly favored gauche-anti conformation about the C(,4')-C(,5') bond. The corresponding ('3)J values for S-adenosyl-L-homocysteine imply a similar C(,3')-exo ribose ring conformation, but the orientation about the C(,4')-C(,5') bond is distributed between two gauche-anti rotamers. The methionine side chain of S-adenosyl-L-methionine has approximately equal populations of rotational isomers about the C(,(alpha))-C(,(beta)) and C(,(beta))-C(,(gamma)) bonds, whereas the side chain of S-adenosyl-L-homocysteine exhibits a conformational preference …

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 …

Isoviscosity Curves In The Analysis Of The Pressure--Temperature Dependence Of Liquid Viscosity., Gayle Nathaniel King

University of the Pacific Theses and Dissertations

The temperature and pressure dependence of liquid viscosity has been extensively discussed in the chemistry, physics, and engineering literature for over half a century. Thus far, theoretical ab initio calculations of temperature and pressure effects on viscosity have been unsuccessful. Therefore there have been numerous attempts to relate fundamental properties of liquid state models with experimental viscosity, temperature, pressure, and density (η,T, P, ρ) data. This work has resulted in many semi-empirical equations expressing η as functions of temperature, pressure, volume, density, chain length, molecular weight, degrees of freedom, etc.

Kinetics And Stoichiometry Of The Aquation Reaction Of Pentaaquodihalomethyl Chromium(Iii) Ions, Mohammad Javaid Akhtar

University of the Pacific Theses and Dissertations

This study was designed to provide information about the mechanisms of pentaaquodihalomethyl chromium(III) ions (halo chloro, bromo and iodo).

...

Mechanisms based on carbonium ion, carbeno and carbenoid type intermediates are proposed. A mechanism based on the nucleophillic attack (S_N2) of water on the carbon center leading to a metal-formyl type intermediate is suggested as best fitting all the criteria observed in these studies.

(see PDF file for additional Abstract as it includes formulas)

Trans Diequatorially Fused Blocking Groups For Glucopyranose Derivatives, Basharat Ali Khan

University of the Pacific Theses and Dissertations

No abstract provided.

Cyclic 4,6-Oxygen-Acetal Derivatives Of D-Glucopyrano-(2,3: 4',5')-2'-Oxazolidinones., Daniel Vernie Robinson

University of the Pacific Theses and Dissertations

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.

3,3-Diphenyl-2-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Allose., Ram Babu

University of the Pacific Theses and Dissertations

A new cyclic protective group has been fused to the cis amino alcohol group of benzyl 2-amino-3,5-o-benzylidene-2-deoxyβ-D-Allopyranoside, by way of a unique rearrangements mechanism. To establish the 2-morpholinone structure, chemical studies, such as reduction and acetylation were conducted.

Comparative spectroscopic studies using ir, pmr, and C-13 nmr confirmed the assigned structures.

The 2-morpholinone ring was cleaved by mild alkaline hydrolysis and could be closed again with acetic anhydride in pyridine. An oxazolidinone derivation of benzyl 2-amino-4,6-o-benzylidene-2-deoxyβ-D-allopyranoside was prepared in a quantitative yield by a modification of a known method.

Protective group properties of the oxazolidinone were studied prior to the …

Comparative Phytochemistry Of Saururaceae Essential Oils., Lohit Venkateswara Tutupalli

University of the Pacific Theses and Dissertations

In view of their native medicinal uses, a systematic investigation of the phytochemistry and Hippocratic screening of three members of the Saururaceac namely, Anemopsis californica, Saururus cernuus and Houttuynia cordata was undertaken.

The Preparation And Characterization Of The Palladium(Ii) And Platinum(Ii) Chelates Of Three Cyclic Tertiary Amino Acids., Floyd Michael Hogue

University of the Pacific Theses and Dissertations

The purpose of this study was to prenare and characterize the palladium (II) and platinum (II) chelates of 1-pyrrolidineacetic acid, 1-piperidineacetic acid, and hexahydro-1-azepineacetic acid.

The ligands were prepared by reacting the cyclic secondary arnines (pyrrolidine, piperidine, and hexahydroazepine) with sodium chloroacetate. The resulting cyclic tertiary amino acids were saponified and, finally, converted to the hydrochloride salts by neutralization with hydrochloric acid.

The chelates were prepared by adding 1.0 millimole of K₂PdC1₄ or K₂PtC1₄ to a solution made by dissolving 2.0 Millimoles of amino acid hydrochloride in 25 ml. of water. The pH was …

The Kinetics And Mechanism Of The Reaction Of Chromium(Ii) With Pentaaquodiiodomethyl Chromium(Iii) And Pentaaquomonoiodomethyl Chromium(Iii) Ions., Ronald Sinclair Nohr

University of the Pacific Theses and Dissertations

Transition metal ions, in low oxidation states, have gained increasing use as versatile reducing agents for a number of organic compounds. The ability of metal ion to act as reducing agents in organic reactions is frequently thought to be due to the formation of intermediates which contain an organic species bound to a metal, although the identy of these organo-metallic intermediates has been determined in relatively few cases.

The purpose of this research was to investigate the kinetics and mechanism of one such reaction: the reduction of iodoform to methane by chromium(II). Two air stable organochromium(III) intermediates were separated and …

Formation And Kinetics Of Dissociation Of Some Pentaaquotrihalomethyl Chromium(Iii) Ions., Sher Khan Malik

University of the Pacific Theses and Dissertations

The present.study was an investigation of the formation and kinetic stability of store complexes contain.ir)ing a chromium-carbon bond in an aqueous medium. An orange-brown pentaaquotrifluoromethylchromium(III) ion was obtained by the reduction of trifluororrethyl iodide with Cr(II) and is the most inert of any organochrotnium(III) complex known. The initial aquation rates of trifluoromethylchromium(III) ion were described by the differential rate law -dln [(H₂O)₅CrCF₃²⁺]/dt = k_{o + k1(H⁺)}

The products of the initial reaction were hexaaquochromium (III), carbon monoxide and HF. The values of k_o and k₁ at …

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

Dipeptide Complexes Of Palladium(Ii) And Platinum(Ii), Lewis Enos Nance

University of the Pacific Theses and Dissertations

Due to recent interest in the role of heavy metals in enzymes. oxygen-carrying molecules. and anticarcinogenic compounds, the study of metal-protein bonding has assumed a new importance. Studies have been made utilizing platinum compounds as anticarcinogenic agents in several different types of cancerous activity. No study of the mechanism by which Pd(II) and Pt(II) compounds exhibit anticarcinogenic properties has been made to date.

The purpose of this research was to investigate the nature of bonding of Pd(II) and Pt(II) with various dipeptides, which were chosen in this study as a basic unit of protein-like material. These compounds have the advantage …

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …

Bromination Of 1,2-Cyclononadiene And 1,3-Dimethylallene, Edward Benny Samuel

University of the Pacific Theses and Dissertations

Much information has been obtained on the orientation of unsymmetrical reagents about substituted allenes. Although hydrogen halide addition to 1,2-propadiene yields 2-halopropenes,^20,31 it has been ample demonstrated, at least in the case of halogenation and oxymercuration of the 1,2-alkyl substituted allenes, that the attacking electrophile ends up in the product attached to the central carbon of the original allenic system. ^{20,22,31,34,38,39,40} Using optically active 1,3-dimethylallene(15) it has been shown that the bromination and oxymercuration of 15 is stereospecific. ^22,39Knowledge of the absolute configurations of the optically active addition products have made it possible to propose a plausible mechanism …

Fluorescence Lifetimes And Quantum Efficiencies Of Some 1,10-Phenanthrolines, Paul John Tabakian

University of the Pacific Theses and Dissertations

Fluorescence properties of fourteen substituted 1,10-Phenanthrolines were determined using two different solvent systems. Hour different sets of experiments were performed in order to measure fluorescence lifetimes, quantum efficiencies, absorption and corrected fluorescence spectra, oscillator strengths, and Stoke’s shifts. Two of the phenanthrolines, the 5-Nitro-1,10-Phenanthroline and the 1,10-Phenanthroline-5,6-Dione, did not fluoresce.

A new equation was developed in order to extract the true fluorescence lifetimes τ from the observed fluorescence output f(t), and the lamp decay function I(t). This equation was [see PDF] where “A” was the weight factor or the normalization constant for the appropriate functions. A test of this equation …

Palladium(Ii) And Platinum(Ii) Complexes Of 2-Cyanophenyl Diphenylphosphine, David Harrison Payne

University of the Pacific Theses and Dissertations

There has been no successful chelation of any phosphorus-acetylenic or phosphorous-nitrile ligand. The objectives of this study were to synthesize such ligands and to study their chemistry and chelating tendencies. The best choice appeared to be the preparation of ortho-substituted triphenylphosphines similar to the chelating ligand allylphenyldiphenylphosphine. The Grignard reactions utilized in the preparation of the olefinic compound could not be used in most cases due to the high reactivity of the acetylene and nitrile function Bromobenzene and iodobenzene have been reacted with alkali metal phosphines under conditions that were probably too drastic for the acetylenic and nitrile functions. There …

Studies Of The Cleavages And Stabilities Of Carbohydrate Epoxides And Epimines, Curtis Alvin Johnson

University of the Pacific Theses and Dissertations

A novel epoxide ring opening of benzyl 3,4-anhydro-2-benzylox-carbonylamido-2-deoxy-β-D-allopyranoside(I) was affected by phenylboronic anhydride in toluene. One of the products was demonstrated to be benzyl 2-benzyloxycarbonylamido-2-deoxy-4,6-0-phenylboronate-β-D-gulopyranoside. Another product isolated, while not identified, had the properties of an anhydro-sugar different from the starting compound(I). Benzyl 6-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-β-D-allopyranoside(II) also underwent epoxide ring opening in a reaction with phenylboronic acid. An isolated product had the properties of a benzyl 2-benzyloxycarbonyiamido-2-deoxy-D-hexoside different from compounds isolate in the reaction of I with the phenyboronate. This indicated the necessity for an unsubstituted 6-OH group in order for the boron compound to be involved in the ring opening. Supporting …

Reactions Of Difunctional Esters With Benzyl 2-Amino-4,6-0- Benzylidene-2-Deoxy-D-Glucopyranosides, Fred Robert Seymour

University of the Pacific Theses and Dissertations

This research is primarily interested in investigating the reactions of benzyl 2-amino-4,6-0-benzylidene-2- deoxy-D-glucopyranoside (I) with various esters. The advantage offered by this sugar is that an alcohol and an amine group are in close proximity, allowing studies of intermolecular vs. intramolecular reactions and observation on anchimeric assistance in intramolecular reactions.

Strained Cycloallenes And Silver Ion Assisted And Unassisted Solvolysis Of Some N,N-Dibromobicyclo(N-3.1.0)Alkanes, Franklin Maurice Boyden

University of the Pacific Theses and Dissertations

The strained cyclic allene intermediates of 1,2-cyclohexadiene, 1,2-cycloheptadiene and 1,2-cyclooctadiene have been successfully generated by the debromination of their corresponding 2,3-dibromocycloalkenes. Evidence for their intermediate existence was obtained by trapping them with the Diels-Alder trapping agent 2,5-diphenyl 1-3,4-benzofuran and by isolating the corresponding addition products.

The goal of this study was to generate the transitory cyclic allenes 1,2-cyclooctadiene, 1,2-cycloheptadiene and 1,2-cyclohexadiene and to investigate some aspects of their chemistry. Evidence for the intermediate existence of these strained cyclic allenes has been found by generating them by the debromination of their corresponding 2,3-dibromocycloalkenes and by trapping the generated cycloallene intermediates with …

The Preparation And Determination Of Some Of The Properties Of The Dicarboxylic Amino Acid Chelates Of Platinum(Ii) And Palladium(Ii), Gordon Harold Williams

University of the Pacific Theses and Dissertations

It is surprising that no one has considered that coordination might have some effect on the strength of the acid group. It is the intent of this study to fill this gap in the knowledge of amino-acid chemistry.

At about the time this study began on the effect of chelation on the strength of the uncomplexed acid group, the next two higher homologs of these dicarboxylic amino acids became commercially available. It was, therefore, decided that the problem of this research should be expanded to include all four of the acidic amino acids.

The research problem was also defined to …

A Short Route To Benzyl Beta-D-Glycosides Of 2-Amino-2-Deoxy-D-Glucose And -D-Allose And Elimination Of The 3-Sulfonate From Benzyl 4,6-O-Benzylidene-2-Benzyloxycarbonylamido-2-Deoxy-3-O-(Methylsulfonyl)- Beta-D-Glucopyranoside, William Denham Rhoads

University of the Pacific Theses and Dissertations

It is one purpose of this dissertation to introduce a facile method for the preparation of β glycosides of D-glucose and D-allose.

It is the second purpose of this dissertation to investigate the preparation of 2-oxazolidinones forming a bridge between C₂ and C₃ of allopyranose. This preparation, along with the facile preparation of β-benzyl glycosides of D-glucosamine and D-allosamine, should lead to compounds which, in a few steps, can conceivably be used for coupling at positions 1 and 4.

An Investigation Of The Feasibility Of Making Radiometric Titrations Of Precipitation Reactions, Harold Elmore Hammerstrom

University of the Pacific Theses and Dissertations

The purpose of the present work was to (1) determine the feasibility of performing radiometric titrations using low activity radioisotopes and inexpensive equipment; (2) develop a workable procedure for performing ·radiometric titrations in the classroom; and (3) assemble the basic radioactive concepts needed so the content could be used in a chemistry course of study.

The limited work done previously with radiometric titrations has used solutions of high specific activity and relatively large volumes of solution. The use of high activity radioisotopes creates problems of radioisotope procurement, shielding, handling and disposal. The use of high activity radioisotopes required special training …

A Polarographic Study Of Substituent Effects In Nickel(Ii)-Complex Ions Of Pyridine And Pyridine Derivatives, Keith Edward Fester

University of the Pacific Theses and Dissertations

The electrochemical technique of polarography was used to study the complexions formed by Ni(II) ion and pyridine compounds. It was of interest to vary the substituent group on the pyridine ring in order to observe the effects on the nickel - nitrogen coordinate bonds.

Electrocapillary Studies Of Reversible Charge Transfer V(Iii)/V(Ii) Electrode, Mohammad Ali Akhtar

University of the Pacific Theses and Dissertations

Electrocapillary equation for an ideal polarized electrode based on Gibb's adsorption equation is appropriately recast into experimentally measurable quantities in order to apply it to a reversible charge transfer electrode.

To calculate the various parameters of the equation developed, experimental details were worked out. For the measurement of Current-time relationship of a single drop, a fast response potentiostat was built by using transistorized chopped stabilized operational amplifiers and precision components in the circuitry with proper compensation for IR-drop in the cell and the electrical double layer capacity. The analysis of I-t curves was done by taking into account the composite …

Determination Of Flow Curves From Capillary Rise Rate Measurements, Richard Lehr Kissling

University of the Pacific Theses and Dissertations

The measurement of viscosity is a common and useful technique for investigating the mechanical behavior of many real fluids. Theoretical interpretations of viscosity measurements have been important in attempts to elucidate fundamental properties of the liquid state. Brush (6) and Bondi (3) give reviews of the current status of attempts to construct theories of liquid viscosity, and it is quite apparent from these reviews that the molecular theory of rheological phenomena is in its infancy.

In addition to the fundamental aspects of viscometry, there are many practical applications to which viscosity measurements are directed (25). One has only to scan …