The need for field and laboratory studies of the physical and
chemical behavior of environmentally significant organic molecules often
poses problems because of the toxicity of the chemical and the difficulty
of detecting it at environmentally significant concentrations.
Two dysprosium tracers, dysprosium (III) trisacetylacetonate trihydrate
and dysprosium(III) trisdibenzoylmethane monohydrate, were...
The design and construction of two new sample injection systems or nozzles, for use with the Oregon State electron diffraction apparatus are discussed. One of these nozzles was intended for use with volatile samples the vapors of which were to be heated or cooled over the range -196 to 540°C;...
The potassium salts of certain 1-vinylcycloalk-3-en-l-ols have
been found to undergo sigmatropic ring expansion rearrangements in
HMPA. Preliminary investigations of several benzo-substituted medium
ring systems were undertaken in order to determine which of these
was best suited for further study. A synthetic sequence leading to
the formation of 5-methy1-6-viny1-7,8,9,10-tetrahydro-6-benzocyclo-octenol,
which...
We have investigated the gaseous structure of cyclohexane-
1,4-dione via electron diffraction. The large amplitude
motion, as suggested from spectroscopic, dipole moment
and earlier electron diffraction data was studied. The
structure was refined in two types of models: a single
"distorted boat" conformer, and a model comprised of a
superposition...
The study of the obstructive factor by Hawkes (11) showed a relation
between the obstructive factor and velocity using a continuous
method. Later, Bowers and Hawkes (12) developed a similar method with
some improvements in the apparatus and found out that the obstructive
factor was not flow dependent. This study...
The atmospheric trace element abundances associated with slash
burning have been measured by instrumental neutron activation analysis
(INAA). On site ground level samples were collected during the slash
burning season using high volume samplers and a cascade impactor. In
addition to the air samples, soil, wood and ashed wood samples...
I. Lithium alkyl and aryl monosubstituted cyclooctatetraenide
dianions (Li₂ C₈H₇-R; R = methyl, n- butyl, sec- butyl, tert- butyl,
phenyl and benzyl) were synthesized by the reaction of the appropriate
organolithium reagent with cyclooctatetraene in diethyl ether or
tetrahydrofuran. The reaction occurred cleanly and with good yield
of lithium monosubstituted...
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 photoelectron spectra of a series of halogenated
molecules have been investigated in the gas phase. Both
core-ionization energies and Auger kinetic energies were
measured to probe the nature of the interaction that holds
a core electron to the molecule.
It was found that satellite structure (shake) could be
used...
The first part of this thesis describes a study of the
characteristics of oxidation of a 1:2 iron(III):thiolate system in
methanolic solution and in water. This system was investigated as a
potential analog for the cysteine- and cysteamine-dioxygenase catalyzed
0₂-oxidation of cysteine and cysteamine, respectively, to the
corresponding sulfinic acids....
The development and applications of a 0.2 cm⁻¹ resolution
Nd-YAG laser powered coherent anti-Stokes Raman
spectroscopy, CARS, spectrometer for gas phase studies is
chronicled in this thesis. Applications including CARS
lineshape analysis, resonant CARS, and CARS of transient
species and excited state molecules is reported.
The intensity of the signal...
The hydroxide ion as a substitutional defect in KC1 can be photo-dissociated
at liquid nitrogen temperature by ultraviolet light. The
photochemistry of this system was investigated by EPR and optical absorption
methods. Theoretical calculations were also performed in an
investigation of the KC1:OH system.
The bleaching behavior of photochemically colored...
Improvements in instrumentation for fluorometric kinetic
measurements and the application of a new intensified diode array (IDA)
rapid scanning system to low level transient fluorescence measurements
are reported. This instrumentation is applied to a new fluorometric
kinetic method for thiamine (TM).
Modifications to the existing fluorometric reation rate instrument
include...
The adsorption of uranium ions from seawater could be of importance
as reserves of uranium are depleted. The structure, chemical
state, and concentration of uranium in seawater have been previously
determined. Uranium exists as a charged ion, UO₂(CO₃)₃⁴⁻. The concentration
in seawater is 3.3 parts per billion.
Previous studies with...
The production cross sections for a number of target fragments
formed by the reactions of 42- and 21- GeV²⁰ Ne and 28 GeV p with ¹⁸¹Ta have been measured. The target fragment radioactivities were
measured by off-line gamma-ray spectroscopy. Details of the measurement
as well as the calculation of the...
Isomerically pure cis,cis,trans-1-pheny1-1,3,5-
heptatriene was prepared and cyclized. Ring closure
was followed by a 1,5 hydrogen shift, and the only product
observed was 1-phenyl -6-methyl -1,3-cyclohexadiene.
Rough first order rate constants for thermolysis and
the hydrogen shift were determined. Kinetic estimates
indicate that the report of disallowed product in a...
The (±) 8,9:13,14-diseco-norestradiol, a large ring hormone
analog, and its related derivatives, were prepared by a ring expansion
approach. The key step of this approach is the establishment of the
benzocyclododecenone system via the Caubere reaction. This step
not only provides a favorable ring size, it also sets the necessary...
A specially designed gas chromatograph with both TCD and FID has
been tested for the measurement of the diffusion coefficients of methane and propane in helium. Knox's arrested elution technique(⁴) was used and yielded a value of 0.6431 cm²/sec averaged with the value
obtained by Yang and Hawkes(⁷). Values of...
An on-line trace enrichment (TE) system, based on high pressure
liquid chromatogroaphy (HPLC) and flame atomic absorption (AA), has
been developed for trace metal analysis. The sample is pumped through
a column filled with a cation exchange resin which traps metal ions.
The ions are subsequently stripped from the column...
A new three-phase argon plasma arc was developed for analytical emission spectroscopy. The power supplied to the plasma arc utilized a simple circuit with three-phase as line voltage stepped down via a transformer to 104Vrms. A three concentric quartz tubing assembly was determined to be the optimum configuration for supplying...
The temporal and spatial characteristics of a laser microprobe plume were investigated using the spectroscopic methods of emission, absorption and fluorescence. The plume was produced by rapid vaporization of a small quantity (1 μg) of a solid sample using a focussed pulsed dye laser (110 MW/cm²). For absorption and fluorescence...
Ultraviolet spectroscopy and dispersive solubility parameters
correlated to the ratios of retention times have proven valuable in
classification of gas chromatography stationary phases by the donor-acceptor
properties. Iodine was directly dissolved into stationary
phases and the absorption frequency shift of complexes was correlated
with the carbon tetrachloride/chloroform retention ratio on...
As with many pairs of metals, the electrodeposition of Pb-Tl, Cu-Cd, and Cu-Ni at solid electrodes yielded partial polarization curves shifted from the polarization curves of the single metals. The curves for the more noble metals (Pb, Cu) were shifted negatively while the less noble metals'(Tl, Cd, Ni) curves were...
Part 1
The concentration of seventeen elements in two species of fungus
which cause wheat bunt disease, Tilletia caries (DC.)Tul. (TS) and
Tilletia controversa Kiihn (DS), were determined by instrumental neutron
activation analysis in 37 TS spore samples, and 31 DS spore samples.
Aluminum was chosen as a soil contamination...
The temporal and spatial characteristics of the plume produced
by a laser microprobe, are dependent upon the composition and pressure
of the atmosphere surrounding it. It has been shown that certain atmospheres
can enhance the analytical signal by increasing the free
atom lifetime.
Improvements were made to the existing laser...
The development and optimization of a fluorometric reaction
rate method for the determination of aluminum is described.
Modifications to existing instrumentation permit automatic
monitoring and reporting of measurement conditions. Automatic
correction of measured analytical signals is provided if monitored
parameters deviate from optimum values. A computer controlled
standard addition procedure...
Integration methods for enzymatic reactions were applied to
transducer response vs. time curves which exhibit maxima, minima or
inflections. The difference between the integral of the time
dependent response and the initial response, often zero, is related
to the initial enzyme activity or substrate concentration. Fluorescence response curves which exhibit...
Various hypervalent iodine compounds were evaluated as reagents
for intramolecular phenolic oxidative coupling. It was found that
phenyliodine(III) bis(trifluoroacetate) was effective for the coupling
of the monophenolic substrate 13a to 14a under neutral conditions.
Vanadium oxytrifluoride and hypervalent iodine compounds were compared
as oxidants for the conversion of 32 to...
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...
Enantioselective epoxidation of crotyl alcohol, followed
by a cuprate mediated methylation, gave a 1:1 mixture of
(2S) -3- methyl -1,2- butanediol and (2R,3S)-2-methy1-1,3-
butanediol. The latter was separated as its 2,4,6-trimethylbenzenesulfonate
derivative and converted via the
iodide to the corresponding phosphonium salt. The separated
butanediol derivatives were independently transformed
to...
The tosylhydrazones of 2-heptanone, 4,4-dimethy1-2-
heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2-
one were synthesized and decomposed under a variety of
reaction conditions: dry lithium and sodium salt pyrolyses,
sodium methoxide thermolyses in diglyme and photolyses of
the lithium salt in tetrahydrofuran. The saturated analogues
2-heptanone tosylhydrazone and its 4,4-dimethyl
isomer afforded the...
Two studies were conducted involving rare earth elements. In the
first study, the use of rare earth diethylenetriaminepentaacetic acid
(DTPA) complexes as stable actiable tracers, a method of stable-isotope
tracing with post-sampling neutron activation analysis, was explored.
The persistence of rare earth DTPA complexes in estuarine waters was
measured in...
An automated instrument based on a single-board microcomputer
was developed for use in voltammetric analyses. Operator input of
numerous experiment parameters allows any type of voltammetric
analysis to be implemented and multiple scans to be run unattended.
A three operational amplifier potentiostat is used to control
the cell voltage and...
Studies of the use of NADH as the monitored fluorophore for enzymatic fluorescence kinetic methods are discussed. Interference studies
for the detection of NADH and the adaptation and optimization of fluorescence kinetic measurements to four serum assays are also described.
A microcomputer-controlled flow injection analysis (FIA) system was
designed and...
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 stereocontrolled synthesis of the southern lactone 17 of
boromycin and of the northern segments of both boromycin and aplasmomycin
are described. The syntheses begin with enantioselective
epoxidation of 3-buten-2-ol (42) to provide the optically active
2(S),3(R) epoxy alcohol 43. The absolute configuration was confirmed
by preparing 43 from (-)-2,3-dihydroxybutyric...
Applications of several methods of coherent nonlinear Raman Spectroscopy have been made in this thesis research. The theory and potential of one of these, Photoacoustic Raman Spectroscopy (PARS), is discussed in chapter two. Experimental results are presented which illustrate the sensitivity of this method and establish sampling conditions for maximum...
A sensitive technique for the determination of As(III) and As{V)
at μ/L and sub-μg/L concentrations from a single sample aliquot
has been developed. This technique is based on the hydride
generation atomic absorption (HGAA) spectrophotometry. The hydrides
of the arsenic species are generated in a reaction vessel by mixing
the...
An instrument was constructed to measure molecular fluorescence (FL) or chemiluminescence (CL) and absorbance (ABS) simultaneously. The lower, middle, and upper portions of the test solution are probed to obtain ABS, FL, and CL data. Optical fibers are used extensively. The ABS and FL or CL spectra are acquired in...
An automated multielement flame atomic fluorescence (AF) spectrometer based on microcomputer control was constructed to determine four elements simultaneously. The instrument employs a multiple exit slit monochromator where the light from various exit slits is directed to a single detector with a mirrored funnel. Each element is excited to fluoresce...
Due to its importance, the phenomenon of hydrogen
bonding has been the subject of much research over the
years. Among the different techniques used to study
hydrogen bonded systems, vibrational spectroscopy is
perhaps the most sensitive because of the striking
changes induced in molecular spectra by the formation of
hydrogen...
Two labelled arginines, DL-[2,3,3,-²H₃]arginine, 8,
and DL-[ ¹³C, 2-¹⁵N]arginine, 9, were synthesized. These
were fed to cultures of Streptomyces griseochromogenes in
order to probe the mechanism of the apparent arginine-2,3-
aminomutase reaction occurring in biosynthesis of blasticidin
S, 1. In previous studies of the enzymes lysine-2,3-
aminomutase and tyrosine-2,3-aminomutase different...
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)...
A unique mass-flow control system for the carrier gas
in gas chromatography is described and evaluated. Carrier
gas flow is controlled by a flow sensor, feedback electronics,
a flow-control valve and a microcomputer. The
flow-rate is monitored by a mass-flow meter by this system
and the flow is adjusted in...
A study of the effects of structural modification at
the alpha position of ethyl 2-bromocarboxylates on their
rates of addition to two alkene pairs was undertaken. In
the competition between 3-propoxypropene and 1-octene at
70°, a 37% increase in selectivity was observed in going
from carboxylates generating primary radicals to...
Bromoalkoxylation of dihydropyran with bromine and 1-borneol, followed by dehydrobromination and epoxidation, afforded trans-2-1- bornyloxy-3,4-epoxytetrahydropyran as a major product. This was treated with sodium phenylselenide to give a 1:1 mixture of (2R,3R,4R)- 2-1-bornyloxy-3-hydroxy-4-phenylselenotetrahydropyran and its (2S,3S, 4S) diastereomer. Elimination of the selenoxide, derived from oxidation of the former with hydrogen...
Four strategies which involve synthetic elaboration of
the shikimate nucleus are discussed. Methyl shikimate was
differentially protected as the 3,4-0-cyclopentylidene ketal
and as the 5- 0- tert- butyldiphenylsilyl ether. The methyl
ester was then reduced with diisobutylaluminum hydride and
the resulting allylic alcohol was oxidized to aldehyde 47
with pyridinium...
A formal total synthesis of the macrolactone pyrolizidine alkaloid (-)-integerrimine (2), from R-(+)-citronellal (93) is described. Aldehyde 93 was converted to exo methylene derivative 94 which was reduced to allylic alcohol 95. The epoxides 96 and 98, obtained in a ratio of 3:1 respectively by Sharp less epoxidation of 95...
An automated on-line ion exchange trace enrichment system has
been developed to improve the detection limits of flame atomic
absorption (AA) spectrophotometry in the determination of trace
metals in natural waters. The sample solution is passed through a
column of Chelex-100 chelating resin by a carrier buffer stream
delivered from...
Plasma sources with multiple electrodes have been developed and
characterized in this research for atomic emission spectroscopy.
Multi-electrode plasma sources use electrodes to shape the plasma in
order to continuously entrain a sample stream in the center of hot
plasma, in a manner similar to an inductively coupled plasma (ICP)...
The target fragment production cross sections, angular
distributions, and range distributions have been measured for the
interaction of 12-16 A MeV³² S with ¹⁶⁵Ho. The fragment isobaric
yield distribution and the moving frame angular distributions have
been deduced from the data. Symmetry properties of the moving frame
angular distributions have...
Early studies on the biosynthesis of the quinoline quinone portion of
streptonigrin, 1, had suggested the intermediacy of novel aromatic amino
acids. In order to test this hypothesis, a series of compounds was synthesized
and tested for potential incorporation. [4-¹⁵N] 4-Aminoanthranilic acid,
4 5 a , [4-² H] 7-aminoquinaldinic acid,...
Avermectins are a group of potent anthelmintic agents produced by Streptomyces avermitilis. They are active at extremely low dosages and are now in commercial use. In this study, the synthesis of two segments of avermectin B[subscript 1a] are described. The synthesis of the hexahydrobenzofuran subunit (segment A) began with the...
The electrochemistry of cadmium at a Reticulated Vitreous
Carbon (RVC) electrode has been studied to determine the suitability of
RVC as a working electrode for the electrochemical preconcentration of
cadmium in the corrosive environment of zirconium dissolved in
hydrofluoric acid.
The electrochemistry in this investigation deals with deposition
of solid...
This thesis concerns itself mainly with analytical methods
development and analytical applications in the field of drug metabolism
studies. The determination of the analgesic pentazocine and its
metabolites in the greyhound are studied.
Pentazocine and all of its possible metabolites are isolated from
the greyhound urine by a the multi-solvent...
The use of gas jets in a sputtering cell makes this direct sampling method practical for atomic absorption and mass spectrometry determinations. With a commercial six-jet sputtering source, the Atomsource (Analyte Corp., Grants Pass, Oregon), that directly atomizes solid samples for conventional atomic absorption spectrophotometers, the sample loss rate for...
Significant figures have been a nebulous area in the physical sciences. The results of a literature survey, and of a questionaire distributed among the Chemistry Department faculty at Oregon State University, revealed widely differing interpretations regarding the proper role of significant figures. The present study has a two-fold nature. First...
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....
Part I describes the synthesis of bis(fac-S)((tris)2-aminoethanethiolatoiron( III))iron(III) chloride. The compound was first discovered during an attempt to prepare a ternary complex of iron, thiolate and pi-acid ligand. The compound is a reasonably air-stable iron(III)-thiolate that contains a linear tri-iron cluster with each iron bridged to the adjacent iron by...
The mycosporins, formerly called P310's are secondary metabolites
of fungi closely associated with fungal reproductive processes that
require light. The structurally related iminomycosporins are found in
marine plants and animals and may also have functions related to
light. In this study, approaches toward the asymmetric synthesis of
the mycosporins are...
The loss of all deuterium labels from previous feedings of [2-²H]-,
[3,3-²H₂]-, and [2,3,3-²H₃]arginines had indicated the possible intermediacy
of β-hydroxy- and β-ketoarginine (30 and 31, respectively) in the
biosynthesis of the streptolidine portion of streptothricin F (la).
In order to confirm or refute this evidence, D,L-[2,3,3,5,5-²H₅]-
arginine (32) was...
The oxide/electrolyte solution interface has been studied experimentally by two methods, and a mathematical model for the interface has been developed. The change in interfacial potential with solution composition was determined through the capacitance of electrolyte/oxide/semiconductor (EOS) structures and the charge through potentiometric titrations of colloidal oxide suspensions. The differential...
The relative rates of hydrogen atom abstraction from a series of
13 homoaryl and heteroarylmethanes by t-butoxy radical were determined at 70°C. The attacking radical was photochemically generated
from di-t-butyl peroxide. A relatively small range of relative rates
(factor of seven) has been found among the compounds studied. The
relative...
A method for the control of absolute stereochemistry in
morphine syntheses has been demonstrated by the resolution
and efficient racemization of the advanced morphine precursor , 9-methoxy-3-methyl-5,6-dihydro-3H-benzofuro[3,2-e]isoquinoline-
7(7aH)-one, I. This was accomplished by the facile coversion of optically resolved I to its ring opened
form, 5,6,7,8-tetrahydro-10-methoxy-3-methyl-7-oxo[1]benzoxonino[
6,7-c]pyridinium tosylate, II, (Equation...
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....
The photochemistry of some analogs of insect growth regulators
(IGR's) was studied. Methyl geranate, TY, was synthesized and the
mechanisms of its photochemical reaction pathways were studied by a
variety of techniques. Direct irradiation of 71 in ether leads to the
formation of five new products: 98, the product of...
The effect of the conjugation with cyclopropyl rings
on the activation parameters for the formation of
carbenes from the corresponding diazo compounds was
investigated using diisopropylcarbene (46), cyclopropyl-isopropylcarbene
(47), and dicyclopropylcarbene (48).
Each of these three carbenes was generated by the
thermolysis of the parent benzenesulfonylhydrazone
potassium salts using DMSO...