This thesis describes a Mossbauer effect and electron
paramagnetic resonance study of iron (III) tetraphenylporphyrinatobenzenethiolate
benzene thiol, an analog compound
for bacterial cytochrome P-450. The compound is unusual in
that it provides a model for the two ferric reaction states
of cytochrome P-450. The iron in the model compound exhibits...
A procedure for evaluating the precision of atomic absorption
measurements is presented and applied to 21 elements under varying
instrumental conditions. The experimental relative standard deviations
(RSD's) in absorbance obtained from repetitive measurements made
with a high resolution voltmeter and on-line computer, are compared
to those predicted by a recently...
An automated radiochemical flow analysis (ARFA) system was developed which integrates chemical and radiochemical techniques into one system through the use of a microcomputer. The operator, through the microcomputer, controls valves and pumps to transfer sample and reagent solutions to counting loops, ion exchange columns and holdup reservoirs. A Ge(Li)...
Basalts of both Eocene and Miocene age from several groups
along the Oregon and Washington coasts have been analyzed for some
major, minor, and trace elements using instrumental neutron activation analysis (INAA). The rare earth element (REE) patterns observed
in these samples are used for comparisons within the groups studied...
The stereospecific reagent-controlled homologation (StReCH) of boronic esters with enantioenriched carbenoid species generated in situ by the addition of organolithium initiators to stereodefined α-chloroalkyl aryl sulfoxides was previously reported. The reaction of an organolithium with an α-chloroalkyl aryl sulfoxide ostensibly generates an α-chloroalkyllithium via sulfoxide-lithium exchange; however, the true nature...
Chalaniline A, an unusual xanthone-like aminofulvene with modest cytotoxicity, and chalaniline B [1-anilino-2,8-dihydroxy-3-(hydroxymethyl)xanthone], an antibacterial aminoxanthone, were previously isolated by Loesgen and coworkers from vorinostat-treated Chalara sp. 6661. Of note, the anilino moiety found within both chalaniline structures originates from biotransformation of the HDAC inhibitor vorinostat (SAHA, suberanilohydroxamic acid) by...
In spite of their importance in many systems, liquid surfaces have been
explored at the microscopic level to a much lesser extent than solids. Most surface
analysis must take place in vacuum, a major drawback for liquids. The technique of
time-of-flight scattering and recoil spectrometry (TOF-SARS) has been applied to...
A series of compounds, 7-8 and 20-25, were tested as competitive inhibitors of 2,5-dihydroxyacetanilide epoxidase I (DHAE I) and DHAE II. A Hammett plot was constructed for each enzyme to determine the effect of electron density on inhibition. DHAE I gave a linear, highly correlated plot (r²=0.91) that signifies the...
A study of the SH and SS content levels during vernalization of
wheat was made. In order to carry out the study, a rapid analytical
technique was worked out which allowed fast sequential analyses of
the samples of wheat tissue.
Two techniques were used: a) an amperometric titration
method and...
The object of this study is the synthesis of trans-cyclopentane-1, 2-dicarboxylic acid. Five procedures designed for the synthesis of
this trans diacid are described in the literature. The procedure
devised by Perkin in 1887, Fuson and Cole in 1938, and by Brenner
in 1961 were investigated to determine which of...
Glucose-1, -2 and -6-C¹⁴ substrates were incorporated into
individual tomato fruits in order to study the catabolic fate of
substrate glucose, especially with regard to the possible occurrence
of triose recombination, as well as to investigate the pathways
leading to the biosynthesis of C₄ acids in the fruit. After metabolizing...
Fungi have long been a prolific source of clinically approved drugs. The antibiotic penicillin, the cholesterol lowering statins, and the immunosuppressant cyclosporine have changed the treatment of human diseases in the last century. Recently, genome analysis of filamentous fungi has revealed that the biosynthetic potential for natural product expression is...
The relative rates of bridgehead hydrogen abstraction from a
series of 1-substituted adamantanes by the trichloromethyl radical
at 40.0°C. has been carried out. Utilizing the Hammett-Taft equation
a p* value of -0.40 was obtained for this reaction. Application
of the Kirkwood-Westheimer model for the transmission of substituent
effects gave an...
The study of natural products (NPs) and their application has shaped humanity. Starting with the idea of using plants as medicine, it has now grown into the science of purifying and identifying organic molecules from nature to study their inherent biological activities. Understanding the molecular structures of NPs is the...
A study was made of the infrared absorption spectrum for
cyanate ion in KCl and KBr host lattices containing small amounts of
calcium or barium ion. Both pellets and single crystals were
scanned during the course of this study. The spectra of the barium
or calcium doped crystals contained many...
The effects of different nitrogen sources on the primary and secondary pathways of Azotobacter vinelandii cells were studied by means of the radiorespirometric method. C¹⁴ labeled glucose and several key amino acids related to the tricarboxylic acid cycle, such as glutamic acid, aspartic acid, alanine, serine and glycine were used...
Many different aspects of the determination of dissolved oxygen
by controlled potential coulometry were investigated to find a means
of measuring the oxygen content of natural waters. Rapid
sampling techniques, simplicity of operation, and rugged structural
features were stressed. Cells were designed to operate by either
internal electrolysis or external...
A series of momochloromethyl arenes and heteroarenes have been reacted
with triphenyltin hydride at 70° C. Under these radical conditions
the only observable reaction is reduction of the starting material to
arylmethane or heteroarylmethane. A significant range of relative rates
(a factor of eighty) has been found among the compounds...
The spectrophone method for the study of vibrational relaxation
has been claimed to possess a distinct advantage over the more commonly
used ultrasonic techniques in that it permits the relaxation of
the various infrared-active vibrational modes in a polyatomic molecule
to be studied separately. A discussion of the rate equations...
The surface areas and pore size distributions of a
series of terrigenous marine sediments were measured by gas
adsorption. The sediment samples were taken from the continental
terrace off the coast of Oregon near Newport.
Sampling stations ranged up to 35 miles off shore between
44°20' and 45° north latitude....
A facile route to bicyclo(2.1.1)hexanes was developed involving
the intramolecular photocyclization of 1, 5-hexadien-3-one to
bicyclo(2.1.1)hexan-2-one. A study of the chemistry of bicyclo-(2.1.1)hexan-2-one was undertaken. Deuterium exchange and borohydride
reduction demonstrated the strain present in the ketone.
Further evidence was obtained from the failure to introduce substituents
alpha to the...
The atmospheric transport of anthropogenic semivolatile organic compounds (SOCs) from Asian sources to the Western U.S. was investigated. In addition, the SOC extraction method was optimized. Hansen solubility parameter plots were used to aid in the pressurized liquid extraction (PLE) solvent selection of air sampling media in order to minimize...
The atmospheric trace element abundances associated with
several major sources of air pollution in Western Oregon, such as the
paper industry, the metallurgical processing industry, the plywood
industry and agricultural field burning have been measured by instrumental
neutron activation analysis (INAA). Air samples were collected
directly from industrial stacks and...
Vanadium pentoxide electrodes were prepared by melting
the powdered oxide around a platinum foil in a pyrex tube. The
electrode was discharged, and the discharge product was studied,
but not identified, by means of chemical and x-ray diffraction analysis.
A study was made of the relationship between the electrode
potential...
The variable length, six-electrode plasma source for atomic
emission spectroscopy described here is operated from three
compact, simple, and inexpensive direct current power supplies. The
vertical arcs formed between the three electrode pairs completely
entrain the sample and are typically operated at 40 V and 20 A.
Three concentric quartz...
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...
A high-spectral resolution laser-excited molecular fluorescence
system was developed that utilizes a pulsed supersonic expansion to
simplify the fluorescence excitation spectra of large, gas-phase
aromatic molecules diluted in an excess of a monatomic gas. A
microcomputer was used to control and synchronize the instrumental
components, which included a Chromatix CMX-4...