A variety of laser spectroscopic methods are employed in this
thesis research for studies of CF₃NO, an interesting model
photodissociative system, and for investigation of low energy rotations
and vibrations of small molecules and low molecular weight clusters in
free jet expansions.
Nonradiative energy decay for electronically excited CF₃NO is...
Contaminant transport in ground water is an important environmental process that
affects a host of natural systems. Transport of contaminants is affected by many
processes, including aqueous complexation, adsorption, and redox reactions. One of the
most important components of an aquifer that controls transport is iron-oxide. In this
study, the...
Quaternary Ammonium Compounds, Qams, are an important class of
chemicals which present interesting challenges to analysts. This thesis
reports results of investigations on uses of ion-pairing techniques for
separations and detection of Qams. Special apparatus for post-column
solvent extraction of liquid chromatographic eluates was developed as
part of this work....
Transition metal oxides are an important class of materials for the wide variety optical, electrical, dielectric, magnetic, and thermal properties observed. Their unique structure-property relationships allow for property tuning and often provide insight into the fundamentals of chemistry. The work in this thesis was focused on the design, synthesis and...
The effect of the proline analogue, L-azetidine-2-carboxylic
acid, on proline biosynthesis in Escherichia coli has been studied.
The analogue inhibits the formation of proline precursor by acting
as a false feedback inhibitor, Analysis of kinetic constants in
whole-cell preparations indicate that the inhibition is noncompetitive.
Comparative inhibitor constants for proline...
A new x-ray source capable of operating at up to 80
watts has been designed and developed, and put to use with
the Oregon State University Cylindrical Electrostatic
Analyzer. The new source produces over four times the
photoelectron intensity of its predecessor, from gaseous
samples, and accommodates a wider selection...
An oscillating plasma glow discharge detector for gas
chromatography is used to obtain fingerprint information
about an analyte by combining both the average cell
current and oscillation frequency signals. Five homologs
each of the n-alkanes, 1-alkenes, 1-alkynes, 2-ketones and
aldehydes are studied. Although triplicate determinations
had some scatter due to...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis in general. The use of strategically-
placed heteroatoms in the cyclizing molecule can influence
the stereochemistry and/or efficiency of an organometallic cyclization
while providing for functionality in the cyclic product.
The work described herein first concerns cyclizations of organolithiums....
Instrumental and radiochemical neutron activation analyses supported by electron microprobe mineral analyses (Paul Warren, University of New Mexico) and petrographic observations are presented for approximately forty individual clasts separated from the Kapoeta howardite. These clasts are classified into eucritic, cumulate-like, mafic (plagioclase ± olivine-bearing pyroxenites), pyroxenite, polymict and/or metal-rich and...
This dissertation demonstrated that the electrical properties of complex oxide-based perovskite materials could be controlled through the careful modification of both material composition and structure. This was first shown through the modification of lead zirconate titanate (Pb(Zr0.52Ti0.48)O3, PZT) solid solutions with bismuth indate (BiInO3, BI) where the relative stability of...
Mitochondria provide energy for biological cells to function, but this process is also a source of oxygen radicals that are capable of damaging nearby proteins. Mitochondrial protein damage can eventually lead to cell death, especially in the case of heart cells, where mitochondria are present in the highest concentrations. As...
Naturally occurring assemblies, such as DNA and proteins, utilize intermolecular forces (i.e H-bonding and van der Waals) to assemble. Utilizing these electrostatic interactions has only just started in the past five decades to be a tool used in synthetic chemistry in what is known as supramolecular chemistry. Supramolecular chemistry has...
An emerging strategy to reducing food waste is converting food processing byproducts to nutritious and inexpensive food ingredients. A relevant food processing waste stream is brewers’ spent grain (BSG), the primary byproduct of beer production. BSG is a promising candidate as a food ingredient because of its high protein and...
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Daniel Smith, Committee Member, representing Department of Food Science & Technology
Polybenzimidazoles were synthesized from 3,3'-diaminobenzidine (DAB) and dicarboxylic acids. The polymerizations using the dicarboxylic acid monomers were carried out in polyphosphoric acid (PPA) and phosphorus pentoxide/methansulfonic acid (PPMA) which acted as the solvent and condensing agent. The resulting polybenzimidazoles had inherent viscosities in the range of 0.12 to 0.84 dL/g....
The techniques of coherent anti-Stokes Raman spectroscopy (CARS)
and inverse Raman spectroscopy (IRS) are used to examine carbon dioxide
aggregation in a supersonic jet expansion. To promote the formation of
small clusters, a BMW injector valve is modified to permit its use as a
pulsed nozzle at very cold temperatures....
The work presented in this thesis deals with the mechanisms by which a vibrationally excited diatomic molecule gives up its energy to a host monatomic lattice at low temperature. The vibrational lifetimes (v"=1) of the metal oxides Ba0 and A10 in their ground electronic states are studied using pulsed dual...
The cocondensation reactions of molybdenum trioxide vapor with
tetraalkoxysilanes, trimethylalkoxysilanes, and hexamethyldisiloxane
at -196°C were investigated. The products from the metal vapor
reactions of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane
were characterized as molybdenum(VI)dioxodialkoxy compounds. The isolated compounds were found to be polymeric in the
solid state by bridging through alkoxide groups....
To determine the impact of emerging environmental contaminants on human and environmental health, quantitative analytical methods are required. Analysis of emerging contaminants is hampered by their widely varying physical-chemical properties. Therefore quantitative analytical methods must be developed to determine the behavior of emerging contaminants in environmental systems.
A quantitative analytical...
The purpose of this investigation was to determine the nature of the
chemical constituents of incense cedar bark with the hope that such an endeavor
would spur future research, development and use of a now neglected
natural raw material.
The bark from nine trees, which were separated into three age...
Eight layered gabbro samples from two layered complexes, two
xenoliths, one basalt from a hot brine area and a standard basalt rock
(BCR-1) were analyzed by RNAA (radiochemical neutron activation
analysis) for 14 trace elements, Au, Ni, Co, Ag, Sb, Se, Zn, In, T1,
Rb, Cs, U, Ba and Sr....
The Diels-Alder reaction represents a promising tool for use in
asymmetric synthesis. The reaction involves a rigid transition state
that facilitates the formation of one diastereomeric transition state
and is reversible. This satisfies two necessary criteria for
asymmetric synthesis.
The Diels-Alder reactions of 1,l-dialkylspiro[2.4]-4,6- heptadienes
with maleic anhydride and p-benzoquinone...
The CARS apparatus at OSU was modified to permit studies in the 0-500 cm⁻¹ spectral region. The new low frequency capabilities were then used to study molecular clusters formed in free expansion jets of carbon dioxide. A strong cluster band was observed at 73 cm⁻¹, with a weaker shoulder at...
Oxide materials exhibit a wide variety of structures and properties. In particular, transition metal oxides tend to be highly stable while exhibiting a wide range of properties that can be used for numerous applications. This work focuses on investigating how the structures’ of 4d and 5d transition metal oxides influences...
Water and methanol adsorption isotherms at 25° and 37° C.
were determined on a series of organo-bentonite clays. The clays
differed in the length of the carbon chain attached to the amine adsorbed
in the cation exchange position. The amines used had carbon
chains of 4, 6, 8, 10, 12,...
This paper describes the synthesis of t-butyl bicyclo[7.1.0]
decane-2-percarboxylate and its photolytic decomposition. The title
compound was found to undergo simple homolytic cleavage when exposed
to light of 2537 A; producing the cyclodecyl radical, carbon dioxide,
and t-butoxy radical. The largest percentage of products arose from
an intimate radical pair...
The thermolysis of trans-1 -trimethylsiloxy- 1-vinylcyclotridec-
3-ene (VI-OTMS) led to the formation of two major products: 4-vinylcyclotridecanone
(VII) and cyclopentadec-5-en-l-one (VIII) after
hydrolysis. Ketone VII is produced by a concerted [3, 3] sigmatropic
shift, while ketone VIII is formed by a [1, 3] sigmatropic shift with
a concerted or diradical...