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The Preparation Of The Coordination Compounds Of Palladium (Ii) And Spermine And Spermidine, Wenli Grace Lee

University of the Pacific Theses and Dissertations

The purpose of this study was to prepare and characterize complexes produced by the reactions of spermine and spermidine with palladium(II) chloride. A first analysis of the problem seemed to indicate that preparation of the complexes should be straightforward and not difficult. Bonding of the nitrogen atoms to the metals allows sterically for formation of two six-membered rings separated by a tetramethylene chain in a spermine complex, and by a six-membered chelate ring in a spermidine complex.

Picosecond Laser Pulse Irradiation Of Crystalline Silicon, K. L. Merkle, H. Baumgart, R.H. Uebbing, F. Phillipp

Electrical & Computer Engineering Faculty Publications

Morphology changes introduced by picosecond laser pulses at λ = 532 nm and 355 nm in (111) and (100) silicon samples are studied by means of optical and high-voltage electron microscopy. Depending on energy fluence, orientation and wavelength, amorphous or highly defective regions may be created. From an analysis of damage thresholds and damage depth distributions it is concluded that melting and energy confinement precedes the formation of the structural changes.

Preparation Of Cationic Polymer Surfaces By Grafting Polymerization, H. Yasuda, B. Sherry, M. A. Ei‐Nokaly, Stig Friberg

Chemistry Faculty Research & Creative Works

A cationic polymer surface with extensive capacity for adsorption of anionic surfactants was prepared by graft polymerization of vinyl pyridine onto a plasma‐treated polypropylene surface. The nitrogen was quaternized in order to obtain the cationic sites. The concentration dependence of adsorption from high eletrolyte solution of the anionic surfactant was similar to the one a solid surface from solutions with no added electrolyte. The hydrophobic contribution to the adsorption was experienced at surfactant concentrations far below its critical micellization. Copyright © 1982 John Wiley & Sons, Inc.

The Anodic Stripping Voltammetry Determination Of Trace Elements In Coal Ash, Jesus Montoya

Masters Theses & Specialist Projects

The application of anodic stripping voltammetry (ASV) to the determination of several trace metals in coal ash was studied.

An ashing and ash digestion method was developed which limited the total salt and acid concentration of the analyte solutions, a necessary step for routine analysis. The simultaneous determination of cadmium, copper, lead, and zinc in eight Pennsylvania State University Coal Bank Samples and in the National Bureau of Standards SRM 1632a coal sample were made. Chromium was separated from the prepared coal ash solutions and determined independently in the form of chromate(VI).

All values determined by ASV methods were in …

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.

Piezomodulation Spectroscopy Of Molecular Crystals. Ii. The Pyromellitic Dianhydride Anthracene Electron Donor–Acceptor Complex, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

Piezomodulated reflection spectra are presented for the crystalline complex of pyromellitic dianhydride–anthracene. Two differently polarized charge transfer transitions are found and their strain sensitivities are obtained. The role of the charge transfer interaction in determining the magnitude of the piezomodulation is assessed. The piezomodulation spectra are found to have the response expected for an oriented gas. Significant enhancement of structure is also observed and is correlated with structure observed at 20 K.

Piezomodulation Spectroscopy Of Molecular Crystals. Iii. The First Singlet System Of Anthracene, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The polarized piezoreflection spectra of the first singlet system of anthracene and their Kramers-Kronig transforms are reported. Exciton energy strain shifts are reported for the b-polarized and for the ac-polarized factor group components. These values are shown to be in good agreement with related experimental data and with theoretical calculations. The piezomodulation spectra significantly enhance structure and are also sensitive to the extent of crystal coupling. Deviations in the measured spectra are observed in the a-polarized spectra from that calculated for the logarithmic derivative. These variances are attributed to coupling with the second singlet of anthracene or …

Piezomodulation Spectroscopy Of Molecular Crystals. I. Methods And Principles, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The effects of piezomodulation on the spectra (particularly reflectivity spectra) of molecular crystals for the strong, weak, and no coupling regimes are considered. The stress or strain modulation of the crystal is shown to affect the dispersion energy and exciton resonance interaction. The experimental approach is outlined. Methods of data analysis are described for obtaining differential changes in the real and imaginary parts of the dielectric function, for determining deformation potentials for vibronic transitions, and for applying the Seraphin coefficients. Previous microscopic theory for interaction of excitons with static lattice deformations is adapted for the modulated case. Application of classical …

Piezomodulation Spectroscopy Of Molecular Crystals. Iv. The First Singlet Systems Of Tcnq And Bdp, J. Merski, Craig J. Eckhardt

Craig J. Eckhardt Publications

The polarized modulated piezoreflection spectra of the first singlet system of TCNQ and BDP are reported. Kramers-Kronig transformations are obtained and polariton energy strain shifts are determined. In contrast to systems with negligible to intermediate coupling, the piezomodulation spectrum for the mixed transverse-longitudinal polaritons show strong deviations from the logarithmic frequency derivative of the corresponding reflection spectra. Progressions in the piezomodulation spectra in the energy region of the stop band are related to multiparticle states. Piezomodulation spectroscopy is shown to exhibit greatest deviation from derivative behavior when solid state effects become extensive.

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 …

23rd Rocky Mountain Conference

Rocky Mountain Conference on Magnetic Resonance

Abstracts and meeting program from the 23rd annual meeting of the Rocky Mountain Conference, co-sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy and the Rocky Mountain Chromatography Discussion Group. Held in Denver, Colorado, August 2-6, 1981.

The Role Of Metals In Carcinogenesis: Biochemistry And Metabolism, K Wetterhahn Jennette

Dartmouth Scholarship

The oxyanions of vanadium, chromium, molybdenum, arsenic, and selenium are stable forms of these elements in high oxidation states which cross cell membranes using the normal phosphate and/or sulfate transport systems of the cell. Once inside the cell, these oxyanions may sulfuryl transfer reactions. Often the oxyanions serve as alternate enzyme substrates but form ester products which are hydrolytically unstable compared with the sulfate and phosphate esters and, therefore, decompose readily in aqueous solution. Arsenite and selenite are capable of reacting with sulfhydryl groups in proteins. Some cells are able to metabolize redox active oxyanions to forms of the elements …

Diagenesis Of Organic Matter In Las Vegas Bay And Bonelli Bay, Lake Mead, James W. Murray, Carolyn J. Jones, Kathy Kuivila, Jeff Sawlan

Publications (WR)

The interstitial water chemistry of the sediments of Las Vegas Bay and Bonelli Bay in Lake Mead has been studied as part of a comprehensive water quality study of those locations. Pore water and solid phase analyses were completed from four stations in Las Vegas Bay and two stations in Bonelli Bay. At both locations the pore water compositions and organic matter diagenesis in the sediments are dominated by sulfate reduction. This major role of sulfate reduction is unusual for lake sediments and reflects the fact that SO₄ is the major anion in the lake water. In addition, gypsum …

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.

Structural And Magnetic Properties Of Co(Urea)₂Cl₂·2h₂O: A Two-Dimensional Lsing System With Hidden Canting, Richard Lewis Carlin, Kyong O. Joung, Andries Van Der Bilt, H. Den Adel, Charles J. O'Connor, Ekkehard Sinn

Chemistry Faculty Research & Creative Works

The characterization of Co(urea)₂Cl₂·2H₂O is reported. The crystal structure at ambient temperatures yields the following information: the chlorine, water, and urea group are coordinated, the urea being bound via the oxygen, to form an octahedral environment about the metal atom. Intermolecular hydrogen bonds between the coordinated chlorine and water ligands produce parallel infinite sheets which provide a two-dimensional exchange pathway. The sheets are separated by the urea ligands and may be considered as magnetically isolated from one another. Crystal data: space group P2₁/c, Z = 2, α = 7.397 (3) Å, b …

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

Archived Theses and Dissertations

No abstract provided.

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 …

Cyclic Voltametry Studies Of Various Ylide Metallocenes, Mark Mojesky

Masters Theses & Specialist Projects

The redox potentials of [Fe(CpSMe₂)₂]²⁺ (CpSMe₂= dimethysulfoniumcyclopentadienflide), [Ni(CpSMe₂)₂]²⁺, [Co(CpSMe₂)₂]²⁺, [Mn(CpSMe₂)₂]²⁺, (CpPPh₃)HgBr₂ (CpPPh₃= triphenylphosphoniumcyclopentadienylide), (CpPPh₃)HgCl₂, and MoPC (PC = phthalocyanine) were examined using cyclic voltammetry (CV). The experimentation was carried out in a temperature controlled environment. With the exception of the mercury and molybdenum complexes, the solvent system consisted of 15 milliliter mixture of acetonitrile and water. Due to the solubility problems of the mercury bromide complex, …

The Anodic Stripping Voltammetric Analysis Of Chromium Using The Hanging Mercury Drop Electrode, John Fugate

Masters Theses & Specialist Projects

The Hanging Mercury Drop Electrode (HMDE) is used in the anodic stripping analysis of ppm concentrations of chromium. The effects of such parameters as ionic strength, polymeric film formation, and the use of the chromate-sodium acetate standard are interpreted in terms of the electro-chemical and physical properties of chromium in the +3 and +6 oxidation states.

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 …

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 …

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 …

Theory And Intuition, E. A. Mccullough Jr.

Faculty Honor Lectures

Among the practitioners of science are people who are called theorists , and this lecture is concerned with the question, Just what is it that a theorist does?

If an experimentalist does experiments, then a theorist presumably does theories. What is a theory? My dictionary defines it as ". . . a system of assumptions, accepted principles, or rules of pro· cedure devised to analyze, predict or otherwise explain the nature or behavior of a specified set of phenomena."

Those who now understand perfectly what a theorist does may stop reading here because everything that follows will be superfluous. For …

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.

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.

Classical Demonstrations Performed To A New Beat, John T. Moore

Faculty Publications

Music can help fill the gaps in time during demonstrations and make demonstrations more exciting.