Lycopodium alkaloids have generated enormous amounts of interest from the scientific community, both as synthetic targets and for their medicinal properties. Herein is described work towards a unifying approach to large segments of the Lycopodium family. An organocatalyzed intramolecular heteroatom Michael reaction method, for the construction of piperidine and piperizine...
Natural products from plants, bacteria, and fungi play an important role in society. Over the last 35 years, natural products and their derivatives have inspired over 60% of all FDA approved small-molecule drugs, and are among the top prescribed therapeutics.1-2 Fleming’s discovery of the fungal antibiotic penicillin started the “Golden...
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...
Dielectrophoresis (DEP) is a separation method in which a non-uniform electric
field is used to induce a dipole moment in a suspended particle. If the polarization
of the particle is greater than that of the suspending medium, the particle will move
towards the region of higher field strength (positive DEP);...
Proteins are essential to all biological systems. Proteins participate in numerous cellular processes by interacting with other proteins, other metabolites and membranes in a dynamic environment. Studying the structural and conformational properties of proteins in the solution phase is necessary to understand their protein folding and interaction dynamics. This research...
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...
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...
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...
Lycopodium alkaloids have shown widespread and noteworthy biological activity, consisting of over 250 known natural products. Moreover, their structural complexity and diversity have attracted considerable attention from numerous laboratories including our own. Recently, we have developed a unified approach that would provides access to numerous, previously unprepared C₁₀-functionalized lycopodium alkaloids....
The 105,000 x g supernatant fluid (S[subscript HS]) from extracts of pea seedlings
(Pisum sativum, var. Alaska) etiolated for 60 hours yielded a
very potent adenosine triphosphatase activity. This activity was designated
as an apyrase when the reaction stoichiometry indicated that
adenosine triphosphate (ATP) was hydrolyzed to adenosine monophosphate
(AMP)...
In this investigation the addition of hydrogen bromide
to 3-methylcyclohexene has been studied in order to see if
the theory of hyperconjugation could be extended to include
olefins of this type. Since the olefin has an equal number
of hydrogens on both carbons carrying the double bond, a
mixture of...
The interactions of a model synthetic liquid fuel reactant (furan) with a model
hydrodeoxygenation catalyst (clean and sulfided single crystal molybdenum)
were investigated using the following UHV tools: Auger electron spectroscopy
(AES), low energy electron diffraction (LEED), and temperature programed
reaction spectroscopy (TPRS). In addition to furan, the reactions of...
In this dissertation, the structural properties, thermodynamics and defect behavior of amorphous metal oxides and polyoxometalates are studied. Amorphous metal oxides have many applications, most notably as a semiconducting material used as the active matrix of thin film transistors. Alas, the amorphous nature of these materials makes studying them rather...
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...
The production of C¹⁴O₂ metabolized from glucose labeled in
specific carbon atoms by homogenates of chick embryonic and adult
heart was compared by the radiorespirometric technique. Homogenates
of early (two to five days of incubation) embryo hearts were
found to utilize the phosphogluconate pathway of glucose catabolism
to a greater...
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)...
New syntheses for 2-bicyclo(3.3.1)nonanone and 7-bicyclo-(3.3.1)nonen-2-one were developed. The saturated ketone was prepared
from phenol and acrylonitrile via a novel intramolecular
S[subscript N]2 cyclization process. A Friedel-Crafts cyclization of 3-(3-cyclohexenyl)propanoyl chloride permitted synthesis of the unsaturated
ketone from 4-cyclohexene carboxaldehyde. The formation of
the bicyclo(3.3.1)nonane rather than a bicyclo(3.2.2)nonane skeleton...
The work described herein details the synthesis and application of
biphenyls that probe the effects of hydrogen, Cl / Br, and methyl substituents
on the aryl ring of the terminal acetylenic carbon. From this work, we
successfully developed the rapid synthesis of phenyl acetylenes in 3-4 steps
from inexpensive commercially...
Fluorinated alkyl substances, which can be persistent, toxic, and
bioaccumulative, have been quantitated in many densely populated and
remote regions, including in air, surface waters, groundwater, and biota;
however, little is known about their transport or behavior in the environment.
Wastewater effluent is one of the principal routes for introducing...
Normal adult rats absorbed and metabolized C¹⁴-labeled acetate
rapidly. The greatest percentage of the administered radioactivity
was recovered in the expired CO₂, however small amounts of radioactivity
were also found in the urine and feces. There were two rates
of C¹⁴O₂ elimination in normal adult rats. The small amount of...
Per- and polyfluoroalkyl substances (PFAS) are a group of contaminants of great concern due to their toxicity and ubiquity in the environment. Remediation efforts historically have focused on granular activated carbon (GAC) because of its low maintenance and relatively low cost. However, GAC is not PFAS selective and is especially...
We have developed a compact micro total analysis system (μTAS) to serve as a platform for in-situ spectrophotometric water quality monitoring. Individual fluidic, optical, and electrical components were designed, developed, and characterized. These components were combined in both an integrated (single lithographic “chip-based” platform) and a modular manner. The microfluidic...
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,...
Ultrafast spectroscopy has recently gained momentum as a powerful, noninvasive characterization toolset capable of studying a diverse array of samples with applications in chemistry, physics, biology, engineering, and more. Two popular ultrafast spectroscopic techniques include femtosecond transient absorption (fs-TA) and femtosecond stimulated Raman spectroscopy (FSRS). The latter of these techniques...
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...
The trans-Pacific atmospheric transport of particulate matter (PM)-bound polycyclic aromatic hydrocarbons (PAHs) to remote sites in western North America has been well documented and has triggered research questions regarding to atmospheric transformation of PM-bound PAHs and the potential impacts on human health from their inhalation exposure. In this dissertation, field...
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....
For a number of reasons, miniaturization of chromatographic columns has been a general trend over the past three decades. Methods designed to enhance selectivity and efficiency can offer improved separation power and speed, expanding on the advantages of miniaturized columns. This dissertation describes novel approaches in this direction, focusing on...
This thesis describes the development of a new enantioselective synthetic method employing chiral cis-2,5-diaminobicyclo[2.2.2]octane-based organometallic catalysts. The significance of this new method to organic synthesis is illustrated with preparation of enantioenriched products that are transformed to important pharmaceutical agents. Chapter 1 provides a brief historical overview of asymmetric catalysis, especially...