When the Affordable Care Act was passed in 2010, eligibility for Medicaid was expanded to include people whose income was less than 138% of the federal poverty level. In 2012, the Supreme Court ruled that states could choose whether to expand their Medicaid programs or not. The objective of this...
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Annie Hommel, Committee Member, representing College of Public Health and Human
Sciences
With Alzheimer’s disease being the most prominent form of dementia, finding potential treatments for the disease is imperative. This study explored the non-steroidal anti-inflammatory drug ibuprofen as a potential treatment to normalize the hyperactive N-methyl-d-aspartate receptor (NMDAR) within the 5xFAD mice early in the disease pathology before cognitive decline. Female...
In this dissertation, the process of computational modeling of amorphous oxide materials is studied. Amorphous oxides have random atomic arrangements with no long-range structural order which makes it difficult to study structure-property relationships. Despite the difficulties, amorphous oxides have great uses as semiconductors and dielectrics in thin-film transistors. The ability...
Gold nanostars are a relative newcomer to the nanoparticle scene, and their unique properties make them very desirable for spectroscopic applications. These nanoparticles, with their sharp tips, create electric field enhancements that interact with light in an advantageous way. This Thesis outlines our in-depth study of gold nanostar synthesis, the...
Ambifunctional axially chiral 2,2',6,6'-tetrasubstituted biphenyls containing nucleophilic (or basic) functional groups juxtaposed with hydrogen-bond donors were synthesized and their properties studied. Applications for the prepared biaryls as potential organocatalysts for enantioselective carbon-carbon bond forming reactions were examined. Processes investigated included: aldol, Michael, nitroaldol (Henry), and Baylis-Hillman reactions.
The novel amidoamine...
Detection technique that proposed utilizing electrochemically controlled, reversible ion extraction into polymeric membrane in an alternating galvanostatic/ potentiostatic mode was introduced. This method is studied in detail to comprehend the advantages of the novel sensor (pulstrode) compared to the potentiometric ion selective electrode (ISE), studies included possible applications and limitations....
Dearomatization reactions exist broadly in biosynthesis and chemical synthesis. The highly functionalized atoms of arenes can be masked by it aromaticity, and upon dearomatization, those reactive atoms can be readily applied to bond formation and further manipulation. The total synthesis of (–)-cephalotaxine and (–)- homoharringtonine is described via an oxidative...
The relative rates of hydrogen atom abstraction from a series of 13 homoaryl
and heteroarylmethanes by the nucleophilic undecyl radical, thermally generated
from lauroyl peroxide, were determined at 70 °C. A reactivity range of 15 was
obtained. Substantial differences in reactivity among isomers were found. The
relative reactivities of the...
Fluorescence has proven to be a robust and powerful method of analysis in numerous fields: forensics, pharmaceutics, geology, food science, and environmental sciences have all developed a large collection of fluorescence instruments and methods to overcome application-specific challenges. Biological applications saw the same development of a fluorescence toolkit with methods...
Direct current conductivity measurements on KC1:O[superscript]= crystals
were used to determine an enthalpy of 0.42 ev for the dissociation for
anion-vacancy-oxide ion complex.
The entropy of dissociation was
found to be approximately -4x 10⁻⁴ev deg⁻¹. The intrinsic "activation" energy was found to be 1.91 ev as compared to 1.95 ev,...
Metabolomics has recently gained momentum in biomolecule research and complements the genomics and proteomics research space. Metabolomics strives to detect, identify, and quantify all metabolites present in biological samples. In particular, biomolecular analysis using ultra-performance liquid chromatography combined with mass spectrometry (UPLC-MS) has become increasingly important for metabolomic analyses. Similarly,...
A comparison was made of the d.c. conductivity of KCI:Pb²⁺
and KCl:PbO single crystals at temperatures greater than 325°C.
The energy of activation was 0.72 ev for all crystals. Lead concentration
was determined by chemical, optical and electrical methods. The
half band width of the UV absorption band at 273...
Recently researchers have discovered that groups of small non-coding RNAs (ncRNAs) play regulatory roles in gene expression and participate in various biological processes. For example, pathogenesis of many diseases, cell cycle regulation, and signaling pathways. Intracellular and live cell imaging of small ncRNA groups will reveal their relative expression levels...
When the dc conductivities of various pure KC1 crystals were
compared it was found that crystals grown under an HC1 atmosphere,
from salt purified by ion exchange, exhibited lower knee temperatures
than any of the crystals studied. These knee temperatures
were found to be approximately 350°C. From this the total...
The simultaneous diffusion of Ca 2+ and Sr 2+ ions in purified
single crystals of KC1 and NaC1 was studied over the temperature
ranges from 451°C to 669°C in KC1 and from 448°C to 683°C in NaCl.
A radioactive tracer technique was used in two types of measurements:
diffusion from...
The investigation
of impurity effects on the properties of alkali
halide crystals has often been difficult because of the variation of procedures used in various experiments.
The purpose of this work is to
develop a self consistent method of measuring the IV dipole polarization properties of single crystals while eliminating...
The first area of investigation involves the electron transport
of sub-mitochondrial particles and their components. The second
area is the synthesis of ATP and other energy linked reactions and
components of the energy conservation and transfer apparatus.
Investigations on the nature of the tetramethyl-p-phenylenediamine
(TMPD) shunt indicated that tetrachlorohydroquinone (TCHQ)...
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...
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,...
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 concept of reducing laboratory operations in scale such that they fit on a microfluidic chip has been met with great enthusiasm. Lab-on-a-chip devices promise to be cost effective to operate due to reduced reagent consumption, have the potential to offer shorter analysis times due to their short path lengths,...
Biochemical studies of phenylmercuric acetate (PMA) and
mercuric acetate toxicity in rats carried out during this investigation
were (1) the metabolism of ²⁰³Hg(Ac)₂ and ²⁰³Hg-PMA within kidney and liver tissues following oral
ingestion,
(2) the effect on some
soluble enzyme activities and determinations of ²⁰³Hg binding in the
enzyme fractions,...
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...
The electronegativities of -SF₅, -CF₃SO₂, and -SO₂F have been measured with gas phase X-ray photoelectron spectroscopy. Of these three groups previously measured values were found only for -SF₅. The electronegativities of -Cl, -Br, -CF₃, and -CF₃, were concurrently measured to determine how the findings of this research compare with other...
White muscle disease or muscular dystrophy of sheep is a selenium
responsive malady common to many areas with an inherent natural
deficiency of selenium in the forage. The disease can be prevented in
lambs by adding trace amounts (approximately 0.1 ppm) of selenium to
the otherwise selenium deficient, forage fed...
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...
Tethering fluorophores on metal nanoparticles for metal enhanced fluorescence (MEF) has attracted a lot of attention from scientists interested in fluorescence based approaches. MEF has many benefits in fluorescence related techniques, because the analytical signal increases and enables potentially lower detection limits or better sensitivity. Many types of nanoparticles have...
As part of the continuing investigation of the thermal cis- 1, 3, 5-hexatriene to 1,3-cyclohexadiene rearrangement, four new trienes and a cross-conjugated pentaene have been prepared and their thermal reactions studied. A new route to the synthesis of highly substituted trienes has been developed. The synthesis of three of these...
The reaction of cyclodeca-1,215triene with mercuric salts
gave only rearranged hydrocarbon, tricyclo[4.4.0.0²'⁴]deca-5ene
in acetic acid. Other catalysts [Rh(CO)₂C1]₂ and AgC10₄ gave
the same rearranged hydrocarbon. The isomerization is proposed
to proceed through a "metalcomplexed" carbenoid intermediate.
The reaction of bicyclo[7.1.0 ]deca-213diene gave
oxymercurated products.
Since their discovery in the 1990s, the great potential of carbon nanotubes (CNTs) has made them a focus of many research endeavors, including their application as components of biosensors. The inherent chemical "inertness" of CNTs makes their application to biosensing a challenge. It is necessary to "decorate" their surfaces to...
The variegated aqueous chemistries of metal cations are applied to the design and synthesis of non-toxic solution precursors suitable for additive printing of large-area oxide electronics. Polycondensation behaviors of aqueous Al+3 and PO4 +3 are manipulated in the deposition of atomically smooth amorphous aluminum oxide phosphate (AlPO) dielectric films. AlPO...
Many pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers
(PBDEs), and polycyclic aromatic hydrocarbons are persistent, bio-accumulative, and
toxic. These semi-volatile organic compounds (SOCs) can undergo atmospheric
transport and deposition in cold, remote ecosystems. A better understanding of their
accumulation in the fish of these ecosystems is important to better predict...
The enantioselective total synthesis of quinolizidine-containing natural product cermizine D and formal syntheses of senepodine G and cermizine C has been achieved. These natural products are members of the lycopodium alkaloids, which have attracted significant attention due to their exciting biological activities and the diverse structural scaffolds. Key steps in...
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...
One post-transcriptional mechanism that regulates the progression of cancer and other diseases involves small 22-23 nucleotide sequences called microRNA (miR). Early detection of small changes in concentration of these biomarkers holds potential to diagnose diseases at their earliest stages. Use of current nucleic-acid based biosensors, like molecular beacons, for in...
Eleven hand specimen whole rock (WR) samples (25-200 g each) and
33 fragments (0.5-0.8 g each) from a single basaltic flow at Picture
Gorge, Oregon were analyzed via instrumental neutron activation
analysis (INAA) for 12 elements (Na, Fe, Cr, Sc, Co, La, Sm, Eu, Yb,
Lu, Hf and Ta). Standard...
A critical study of the cold vapor atomic absorption and fluorescence instrumentation for the analysis of mercury is described. Some of the important modifications involve the reduction vessel, absorption cell, fluorescence cell, and radiation source. The new modified systems have much greater calibration sensitivities and lower detection limits than those...
A novel acyl protecting group for cytosine and adenine has been prepared
from 4-( chloromethyl) benzoic acid. Reaction of the acid with morpholine produces
4-( 4-morpholinyl )methyl benzoic acid which is converted to it's acid chloride
with thionyl chloride. This may be used to acylate cytidine and adenosine under
standard...
Oxidative phosphorylation and related reactions, particularly as
affected by 2, 4-dinitrophenol (DNP), were studied with mitochondria
and submitochondrial particles isolated from the flight muscle of the
blowfly (Phormia regina) and housefly (Musca domestida). In the
presence of a phosphate acceptor, the mitochondria oxidized pyruvate
rapidly, and this was tightly coupled...
A new approach to the discovery of high absorbing semiconductors for solar cells was taken by working under a set of design principles and taking a systemic methodology. Three transition metal chalcogenides at varying states of development were evaluated within this framework. Iron pyrite (FeS₂) is well known to demonstrate...
Preparation of a cytochrome c-cytochrome oxidase complex
was achieved, using crystalline beef cytochrome c and purified
cytochrome oxidase from beef heart muscle, or from the
Keilin-Hartree preparation. Succinate oxidase was reconstituted
with the complex.
A mixture of cytochrome oxidase, solubilized with nonionic
detergent, and excess cytochrome c was exposed to...
Small molecule drugs have been instrumental in our fight against diseases, beginning when some of the earliest ancient cultures used plant remedies to treat illnesses. More recently, the skill of isolating and characterizing the active ingredients within bioactive plants and microbial extracts has led to the isolation and design of...
The atmospheric trace element abundances associated with "indoor"
and '"outdoor" air particulate have been measured for university chemistry
laboratories, typical homes, modern office buildings, hospital and
automobile repair garages in a rural setting (Corvallis, Oregon) and
modern office buildings in an urban setting (Portland, Oregon). Samples
of atmospheric particulate matter...
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In recent decades, there has been increased attention on human exposure to, and subsequently toxicity of, Polycyclic Aromatic Hydrocarbons (PAHs). PAHs are widespread organic pollutants and some have been shown to be toxic, carcinogenic and mutagenic. This research was focused on understanding the link between global PAH emissions and lung...
Oxidative stress is recognized as an important underlying factor in the
pathogenesis of many degenerative diseases as well as normal senescence. The
free radicals, reactive oxygen species (ROS) and electrophiles produced during
oxidative stress are capable of modifying nucleic acids, lipids and proteins. There
are a variety of oxidative modifications...
Per- and polyfluoroalkyl substances (PFAS) are a group of anthropogenic compounds gaining notoriety as contaminants of emerging concern. With the frequent detection of PFAS in the environment, drinking water, and consumer products, awareness and concern from the public regarding PFAS is increasing. The two most notorious PFAS are perfluorooctanoate (PFOA)...
Early studies on the biosynthesis of Sarubicin A, 1, had suggested the
intermediacy of the novel aromatic amino acid 6-hydroxyanthranilic acid,
17. To investigate the biosynthetic steps beyond 17, [¹³C-¹⁵N carboxamide]
6-hydroxyanthranilamide, 27a, was synthesized, and fed to fermentations
of Streptomyces helicus. Incorporation of 27a into 1 provided suggestive
evidence...
Apparel fashion is a daily component of society that transcends generations and cultures.
The purpose of my research was to analyze the garment structure and construction of two
separate but comparable garments in style, function, and content - one from the 1910s
and one from 2015. Using the New Brunswick...
The observed and calculated structural parameters of three systems
of phosphatidylcholine bilayers in fully-hydrated multilamellar
vesicles (MLVs) were determined using x-ray diffraction techniques.
The analysis used the x-ray reflections from the low-, intermediateand
wide-angle regions of the diffraction patterns in the subgel, gel,
rippled and fluid phases to determine the...
Two related techniques, based upon ion-exchange solid phase extraction, have been
developed for the determination of arsenic speciation. The inorganic arsenic species
arsenite (As(III)) and arsenate (As(V)) are separated by anion-exchange and detected with
graphite furnace atomic absorption spectrophotometry (GFAAS) with a nickel matrix
modifier. The first separation technique, which...
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...
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....
Refractory inclusions from Kaba (CV3) chondrite were studied by
instrumental neutron activation analysis (INAA) and electron probe
microanalysis (EPMA). The inclusions observed cover a wide range of
chemical patterns, mineral assemblages and textures, indicating the
complexity of early solar nebular conditions. The elemental
abundances normalized by Cl chondritic abundances vary...
State-of-the-art, high-resolution mass spectrometry techniques for acquisition of metabolomic and lipidomic data coupled with advanced computational methods provide new opportunities for interpreting large and complex datasets and comprehending the underlying biological processes of diseases. Both metabolomics and lipidomics strive to obtain comprehensive analyses of small molecules, i.e., metabolites and lipids,...
In this dissertation, I describe the experimental investigation in electron diffraction of molecules in superfluid helium droplets. The project is part of an overall scheme called ‘single molecule serial electron diffraction imaging’ (SS-EDI), with the ultimate goal of building an apparatus to determine atomic structures from oriented macromolecules. In SS-EDI,...
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....
The adduction of proteins and other biomolecules by electrophilic lipid peroxidation products such as 4-hydroxy-2-nonenal (HNE), 4-oxo-2-nonenal (ONE), malondialdehyde (MDA) or acrolein (ACR) is thought to be an initiating and/or propagating factor in the pathophysiology of several diseases such as atherosclerosis, diabetes, Alzheimer's, Parkinson's and other age-related disorders. The identification...
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...
In this dissertation, I describe spectroscopic studies of jet-cooled polycyclic aromatic hydrocarbons (PAH) and one nitrogen substituted PAH (PANH) using pulsed field zero kinetic energy (ZEKE) photoelectron spectroscopy and resonantly enhanced multiphoton ionization (REMPI) spectroscopy. Recently, there has been a demand for far-infrared (FIR) spectral information of astrophysically relevant molecules...