Iodine-129 is a key risk driver at sites where nuclear materials have been fabricated or processed, and it is a predominant isotope of concern in long-term waste storage strategies. I-129 exists primarily as iodate in the subsurface at the Hanford Site in south-central Washington State. Between 15 and 40% of...
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...
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...
Six organoclay complexes have been studied in terms of their
selective adsorption from binary solutions of methanol and toluene.
Analyses are based on differential refractometry methods. The
isotherms were of the usual "S" type. The crossover points reveal
trends in the organophilic nature of the interlaminar surfaces in
these clay...
The tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript...
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...
The present study has consisted primarily of an investigation
of the rates of isotopic sulfur exchange between sulfur dioxide and
various sulfur (VI) solutions, both 100% H₂SO₄ and, in particular,
related ammonia-containing sulfur (VI) solutions. One of the main
objects of the work was to obtain a comparison between exchange...
A spectrophotometric study has been made of catalysis of the decomposition of sulfuryl chloride in carbon tetrachloride solution to an equilibrium mixture of sulfuryl chloride, sulfur dioxide and chlorine. The catalysts were activated charcoal, acetonitrile and 18-crown-6 polyether. A weak acetonitrile-sulfur dioxide complex also was established; formation constants found at...
Two framework oxide materials of the MO₃ network type have been synthesized and structurally characterized by synchrotron and X-ray powder diffraction and the Rietveld method in the temperature range 25~500 K. The results show one of them to be a low thermal expansion material. Theoretical studies of negative thermal expansion...
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 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...
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...
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 results of the research presented in this work are related to synthesis and investigations of novel color inorganic pigments having various structures and shades. Inorganic pigments play a major role in contemporary life. They are used in paints, rubber, plastic, cosmetics etc. Searching for new, stable, environmentally benign and...
High-precision instrumental neutron activation analysis has
been used to determine Al, Na, Mn, Sc, Cr, Fe, Co, and Ni in a
suite of more than 500 chondrules from 26 distinct meteorites. These
meteorite specimens represent the H, L, LL and C chemical classes
and most of the petrologic types. In...
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
investigation was
made
into certain
aspects
of
protein
synthesis
at
different
developmental stages
of the
flesh fly
Sarcophaga
bullata.
This
included
measurements
of the
incorporation of
labeled
amino
acids into
protein
by intact cells
from
a
single
organ, the
larval
fat
body,
and
a
study
of
amino
acid
activating...
We report the use of MIL-120 as a water-stable and cost-effective metal-organic framework (MOF) for selectively capturing CO₂ from wet flue gas. Synthesized using inexpensive and environmentally benign reagents in water, MIL-120 possesses one-dimensional pores decorated with hydroxyl-bridged Al(III) ions and benzene rings with an interstitial spacing of 4.78 Å....
......................................................................................43
Figure S3. The N2 isotherms at 77 K obtained for MIL-120(Al) and MIL-120(Ga
An attempt has been made to elucidate the biosynthetic precursor
of ethylene in the mold P. digitatum. By application of basic
radiotracer methodology and the utilization of several specifically
labeled radiochemical substrates, it has been possible to demonstrate
that the internal carbon atoms of C-4 dicarboxylic acids such
as succinate,...
The study of diffusion coefficients of n-alkanes and other organic compounds in silicones is undertaken by gas-liquid chromatography. About 0. 3% of stationary phase is coated on glass bead support so that the only significant source of peak spreading is due to slow liquid phase mass transfer. Diffusion coefficients are...
The relative rates of hydrogen abstraction from 1-phenylalkanes and a,w-diphenylalkanes using N-bromosuccinimide and bromotrichloromethane were determined at 70°C. In both cases the reactions were photoinitiated. Only benzylic bromination was observed. The 1-phenylalkanes reacted with both reagents to give rates largely independent of substrate. Similarly, the rate of the reaction between...
Bicyclo [6.1.0] non-4-ene was prepared by two routes; (1) reaction
of cis-cis-1, 5-cycloöctadiene with methylene iodide and zinc-copper
couple, (2) sodium-methanol reduction of 9, 9-dibromobicyclo-[6.1.0] non-4-ene. The bicyclononene was characterized by its infrared
spectrum, nuclear magnetic resonance spectrum and common
physical properties. The olefin was hydrogenated to bicyclo [6.1.0] -...
The formation of cytosine hydroperoxide was detected in
aqueous cytosine solutions irradiated with Co-60 γ-rays at pH 2.
The nucleotide of cytosine, cytidylic acid, forms a hydroperoxide
which was detected in neutral solution. The stability of the hydroperoxides of cytosine, thymine, and their nucleotides was found to
be a function...
Polycyclic aromatic hydrocarbons (PAHs) are a group of environmental contaminants consisting of fused benzene rings. Parent-PAHs, methylated-PAHs (MPAHs), and PAHs with molecular weight of 302 a.m.u (MW302-PAHs) are considered as unsubstituted-PAHs. These unsubstituted-PAHs undergo transformation reactions resulting in the formation of PAH-transformation products (PAH-TPs), or substituted-PAHs, including nitrated-, oxygenated-, and...
The subject of this PhD thesis is part of a research domain of great present interest in new semiconductor materials for photovoltaic and thermoelectric applications. This domain contains the elaboration and the study of both Cu-based chalcogenides bulk and thin-film samples, driven by materials design principles.
One of the most...
Optimization of the galvanovoltammetric determination of dissolved
chlorine in a flowing stream was achieved through the use of
an analog computational device and improvements in the design of the
galvanovoltammetric cell and accompanying electronic circuitry. An
analysis system, applicable to industrial use over a range of flow
rates and dissolved...
The infrared spectra of the metaborate monomer and trimer
ions in NaC1, KC1, and KBr were studied. These spectra contain
bands due to the trimer in solid solution, in a second phase of the appropriate
potassium or sodium salt, and perhaps on adjacent lattice
sites. Furthermore, complex equilibria exist between...
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...
Neptunium, with its rich redox chemistry, has a special position in the chemistry of actinides. With a decades-long history of development of aqueous separation methods for used nuclear fuel (UNF), management of neptunium remains an unresolved issue because of its not clearly defined redox speciation. Neptunium is present in two,...
The satellite structure ("shake-up") present in the X-ray
photoelectron spectra of several planar molecules containing
double bonds has been investigated in the gas phase.
This set consists of three five-membered heterocyclic
molecules, ethylene and two of its fluorinated analogs, and
benzene with three of its fluorinated analogs. In addition,
core...
The photoelectron spectra of a series of ketone
compounds have been investigated in the gas phase. Core
ionization energies were measured to probe the effects of
molecular size and connectivity number on core ionization
energies.
It was found that core ionization energies roughly
decrease with increasing connectivity number as expected....
The core-electron ionization potentials for mono- and
di(trifluoromethyl)benzene, for chlorofluoromethanes and for
chlorine have been measured in order to give information on
the electron distribution in these molecules and to investigate
differences between the inductive effect of fluorine
and that of CF3. For trifluoromethylbenzene the measured
ionization potentials in eV...
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants formed from the incomplete combustion of organic material. These contaminants are of concern because of their widespread presence in the environment and toxic properties. In addition, PAHs encompass a class of diverse compounds with varying physicochemical properties and exist in the environment as...
The structure–property relationships of solid solutions within the YbFe₂O₄ family of compounds have been studied in relation to their optical, dielectric and magnetic properties. This family of compounds is of recent interest because of the trigonal bipyramid coordination that is rarely observed in transition metal oxides. The systematic study of...
Nowadays selective separation processes are sought after more than ever before. They are indispensable to meet the growing demand for individual rare earth elements, minor actinides partitioned from fission-produced lanthanides, as well as, overall, more concentrated and high-purity products. This research focuses on such separation techniques as solvent extraction which...
Levels of activity of glucose-6-phosphate- , 6-phosphogluconate- , and isocitric- dehydrogenase were measured in the
soluble and particulate fractions of heart, brain and liver at
several ages throughout the development of the chick embryo.
Compared to isocitric dehydrogenase, levels of glucosesphosphate-
, and 6-phosphogluconate- dehydrogenase are generally
low. This suggests...
It is the responsibility of humans, as environmental stewards, to monitor our impact on the environment so that efforts can be made to remediate the effects of our actions and change behaviors. To better understand our environmental footprint, sensitive and simple analytical methods are needed to quantify the contaminants that...
The photolysis of the aqueous thymine system has been investigated
at 214 nm, 229 nm and 254 nm at room temperature. Products
of photolysis have been identified as hydrogen peroxide, 6-hydroxy-5-
hydroperoxy thymine and tentatively 5-hydroxy-6-hydroperoxy thymine.
These together with thymine loss, were determined quantitatively
under a variety of conditions....
This research was on the irreversible oxidation of trimethylamine by copper(II) chloride, which takes place at temperatures of about 75° and higher. The coordination of trimethylamine by copper(II) chloride, which is a preliminary reaction to the oxidation, was studied at 0°. The coordination of trimethylamine by the potential reduction product,...
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...
Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis. The reaction involves exothermic
consumption of intramolecular double bonds via insertion
into a carbon metal sigma bond. This represents an intramolecular
example of the reaction type responsible for metal catalyzed polymerization
of olefins.
Organolithium reagents were found to cyclize...
This thesis investigated on the dehalogenation of 2, 4-
dichloropyrimidine in various different conditions. These conditions
were changed by varying the solvents, the amount of catalysts and
the hydrogen chloride acceptors in order to study the effects on the
yields.
It was found that the ether-aqueous sodium hydroxide medium
with...
Copper in blood and liver can be divided into several fractions.
Copper in blood is about evenly divided between erythrocytes and
plasma. Normal concentrations for most species range between one and
two parts per million. Plasma copper is mainly a copper protein,
ceruloplasmin and a loosely bound form, reacting directly...
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....
Structure-property relationships have always underpinned the field of solid state chemistry; dependable structural descriptions are integral to understanding and controlling the physical properties of inorganic compounds old and new. While a handful of crystal structures are celebrated for their versatility, flexibility, and functionality, the existence of more exotic structures is...
Three types of experiments were designed to further characterize
the tryptophan decarboxylating enzyme of Reed and Crecelius
(1967).
1) Light inhibition studies were made with etiolated pea seedlings
to determine the in vitro response of the tryptophan decarboxylating
enzyme. Assays of indoleacetic acid oxidase (IAA oxidase)
and guaiacol-active pea seedling...
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...
Oxides of post-transition metals often show unique structures and properties due to the presence of lone pair electrons and the diffused s orbitals. The present work focuses on synthesis and characterizations of oxides containing Te, a heavy post transition metal.
New series of pyrochlore oxides of the formula Cs(M,Te)₂O₆ (M...
Previous investigations of the biosynthesis of sterols by the
arterial wall have shown that the intact aorta is capable of low level
incorporation of labeled precursor into a sterol digitonide. The biosynthesis
of sterols and related lipids by a cell-free preparation of
bovine aorta was investigated in the present study....
The retro-ene reaction of 2-vinylcyclohexanols occurs readily
in the vapor phase at 400-450° producing unsaturated carbonyl
compounds in good yields. The starting- materials were prepared in
general by the carbenoid addition reaction of ethyl diazoacetate,
appropriately substituted cyclohexene, and copper catalyst to
produce bicyclic esters which were reduced to the...
Alkylation of propylene oxide with 2-lithiofuran gave alcohol I,
which was smoothly converted to acetylfuran II. hydrogenation of II
over rhodium on charcoal followed by Jones' oxidation afforded ketone
III. Further transformation into IV was accomplished via a Wittig
reaction followed by saponification with methanolic sodium hydroxide.
Hydroboration of the...