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...
Studies toward the total syntheses of highly potent cytotoxic alkaloids
including the bromopyrrole alkaloids and indole alkaloids were conducted and are
described. Studies carried out in the course of this dissertation consist of five total syntheses of natural products that include bromopyrrole alkaloids nagelamide A, D and agelastatin D as...
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....
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...
Rat liver microsomes are shown to contain an enzyme system
which converts the cyclodiene insecticides, aldrin, heptachlor and
isodrin to their corresponding epoxides, dieldrin, heptachlor epoxide,
and endrin. The microsomal fraction of 450 milligrams of liver from
male rats epoxidates 80 percent of a 20 to 50 microgram aldrin substrate...
The aqueous chemistries of two transition metal cations, Zr⁴⁺ and Nb⁵⁺, are examined and then used to develop inorganic precursor solutions. The oxides of these cations (ZrO₂ and Nb₂O₅) are deposited and characterized, and their morphological and optical properties discussed. Due to the obstacles created by niobium's aqueous chemistry, an...
An intermediate of oxidative phosphorylation was apparently
solubilized from cabbage mitochondria. The method of solubilization
used primarily was extraction of a mitochondrial acetone powder
with 0.1 M glycylglycine, pH 7.4, at 4° C. The intermediate
betrayed its presence by causing the transfer of Pi³² to ADP with
the resultant formation...
This dissertation demonstrated that the electrical properties of complex oxide-based perovskite materials could be controlled through the careful modification of both material composition and structure. This was first shown through the modification of lead zirconate titanate (Pb(Zr0.52Ti0.48)O3, PZT) solid solutions with bismuth indate (BiInO3, BI) where the relative stability of...
Analytical techniques are utilized in a wide variety of applications. Traditionally, analytical measurements are achieved by trained personnel in a laboratory setting using expensive scientific instruments, which limits their applicability in resource-limited areas and point-of-care applications. Therefore, the concept of enabling these laboratory-based qualitative and quantitative assays in microfluidic device...
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...
Organic compounds which contain one or more nitrogen atoms are especially important as they are disproportionately represented among biologically active molecules. As a result, significant effort has been focused on the development of methods for the synthesis of nitrogenous molecules. We identified the aminal as an under-explored functional group. Despite...
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....
Widespread installation of renewable energy sources, such as wind and solar, has been delayed by the lack of suitable stationary energy storage solutions. Current large-scale technologies, such as pumped hydro and compressed air, are geographically restricted. This is where electrochemical energy storage - batteries or hybrid capacitors can play a...
Water is an absolute necessity for life as we know it. It provides a useful medium in which chemical reactions take place that allowed for the development of single cellular organisms. When combined with the evolutionary accident that was pho- tosynthesis, water became not only a useful medium chemical reactions,...
Inorganic structures play an important role in materials due to their versatility and diversity. A complete understanding of the structure of a material is vital to enhance the creation of new materials that fill voids in research. The rational design of these compounds is driven by the exploitation of structure-property...
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...
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...
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...
Studies were undertaken to determine the extent and rate of
binding of Hg-203 labeled phenylmercuric acetate and mercuric ace
tate in rat kidney and liver slices and their subcellular fractions
after 37°C incubation of the slices in Krebs-Ringer -phosphate solutions
containing the mercurials at 10⁻⁴ molar. A fast and parallel...
This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
This study aimed to explore the relationship between urinary cortisol levels and proximity-seeking behavior in shelter cats and the impact of socialization programs on these two factors. A Spearman’s correlation test found no correlation between cortisol levels and proximity-seeking behavior in shelter cats. Fisher’s 2x2 tests confirmed that the changes...
Metal-organic polyhedra (MOPs) are discrete molecules comprised of a metal and interconnecting ligands. The resulting MOP structures are porous cages, and to date, they have shown great promise toward gas capture. Ammonia is a hazardous gas that is produced in enormous quantities for use in fertilizers. In this talk, I...
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....
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...
PART I. A deuterium exchange analysis of 2,5-dihydroxyacetanilide (5) in the absence and presence of DHAE II was performed to test the nucleophilicity of the substrate in the absence and presence of catalyst. In addition, inhibition studies using 1,4-dihydroxybenzene were performed to determine the role that the N-acetyl side chain...
Coded metrics that compare representations of structures within the human body to evaluate their similarity are considered useful for planning radiation therapy on cancer targets. However, existing metrics fail to take into account the dose of radiation that will be received by both the target, and surrounding non-target tissue, during...
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...
Verrucarol is the sesquiterpene portion of a number of macrocyclic di- and triesters of potential medicinal importance. In this study, a novel approach to the synthesis of this fungal metabolite is presented. An A-B-C route was investigated in which C-3 and C-4 of the C-ring were emplaced using a [2+2]...
Solid-state amorphous materials show amazing promise in thin-film electronics. The interface-to-bulk ratio of thin films makes interfacial chemistries of these systems of utmost importance. Thin films of amorphous metals, dielectrics and semiconductors have novel chemistries that are not only based upon their elemental constituent makeup, but also based upon 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...
In this dissertation, the primary objective is to discover more sustainable electrode materials and study new reaction mechanisms using aqueous electrolytes. The first study conducted reveals a reversible conversion reaction from copper to Cu2CO3(OH)2. The reaction mechanism uses OH- and CO32- as charge carriers at the cathode. The results open...
Pelargonium graveolens Ait., rose geranium, contains several oxygenated monoterpenes, most of which are related to each other structurally. In this work, the metabolism and interconversions of these terpenes was investigated. A chromatographic analysis of geranium oil was performed initially for the purposes of identifying the terpenes and determining which chromatographic...
The spectrophotometric method for the determination of the
acid nonextractable flavin in the proteolytic digest of the trichloroacetic
acid precipitate from the heart muscle preparation has been
examined for the interference of the degraded hemeproteins. The
proteolytic digest was chromatographically separated into the heme
and flavin fractions. Spectrophotometric determinations made...
The effects of different levels of copper in the diet on growth
rates, blood and liver copper concentrations, hemoglobin levels,
and cytochrome c oxidase activities were determined in the cotton
rat. The response of the cotton rat to different levels of copper was
analagous to that of the common laboratory...
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...
Major and minor minerals have been separated from
three L-6 chondritic meteorites (Alfianello, Colby (Wisconsin),
and Leedey). Olivine, hypersthene, diopside, feldspar,
troilite, chromite, phosphate minerals, and metallic
minerals were analyzed for major, minor and trace elements
using instrumental neutron activation analysis and radiochemical
neutron activation analysis techniques. Concentrations
df the...
Steroid carbenes have been investigated as synthetic intermediates.
Basic decomposition of 4-en-3-one tosylhydrazones (and
other A-ring systems) gives varying amounts of 2, 4-dienes, and
solvent derived products with diglyme, heptane, tetrachloroethylene,
carbon tetrachloride, benzene and cyclohexene. A method for
separating complex product mixtures was developed and a study of
the...
The incorporation of europium and dysprosium in potassium
chloride crystals was investigated. The crystals were prepared by
the Kyropoulos method from melts containing the rare-earth chlorides.
The concentration of these rare-earth ions in the crystals was determined
by neutron-activation analysis. The distribution coefficient of
europium and dysprosium between the molten...
The methanolysis of phosphorus trichloride coordinated to nickel
(0) has been studied. Free phosphorus trichloride reacts with methanol
to give dimethyl hydrogen phosphonate, methyl chloride, and hydrogen
chloride. The reaction involves a rearrangement on phosphorus using
the lone pair, in which the coordination number increases from three
to four. In...
An automatic digital titrator for use in potentiometric titrations
is described. The automatic titrator described provides
a permanent digital and analog record of all titrations. The modular
units which combine to form the automatic titrator are described
individually. Accuracy achieved by the titrator on successive
acid-base titrations of ammonia in...
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...
More than 30 members of the diverse amphidinolide family of biologically active macrolides have been isolated over last three decades. From this family, amphidinolides C and F stand among the most complex and densely functionalized affiliates. Recently, we have accomplished the first total synthesis of amphidinolide F. The all-carbon framework...
In Part I, (4S,5R)-4,5-dimethyl-4-phenylcyclohex-2-enone (19a) was prepared in 73% yield with high enantio- and diastereo-selectivity (er > 98:2, dr > 20:1) on a multigram scale by a Yamada-Otani condensation between (E)-pent-3-en-2-one and 2-phenylpropanal catalyzed by a sulfonimide derivative of (S)-proline (18, HuaCat®). Synthetically useful transformations of the cyclohexenone product 19a...
In this Dissertation, the mechanism and stereomechanics of complex organocatalysis and reaction processes are disclosed. The technologies and protocols currently being developed and utilized to efficiently investigate these systems using theory are highlighted.
A detailed computational study of peptide-catalyzed acylations is disclosed. In particular, the magnitude of all possible non-bonding...
The infrared spectra of liquid and solid films of
formaldehyde were taken over the range of 35 to 4,000 cm⁻¹
using Beckman IR 7 and IR 11 spectrometers. A new overtone
band and a new combination band were found as well as three
fundamental peaks due to lattice vibrations and...
The distribution of hydrophobic ionogenic organic compounds
(HIOC's) between aqueous and nonaqueous phases has been
investigated. The HIOC's are aniline and methyl substituted
anilines. The aqueous phases are methanol-water mixed solvents with
varying pH and ionic strength. The nonaqueous phases are silica and
alkyl derivatized silica with ethyl- (C-2), octyl-...
Contaminant transport in ground water is an important environmental process that
affects a host of natural systems. Transport of contaminants is affected by many
processes, including aqueous complexation, adsorption, and redox reactions. One of the
most important components of an aquifer that controls transport is iron-oxide. In this
study, the...
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,...
At liquid nitrogen temperature the spectra of sublimed
films of NH₄NCS, both as phase I (the usual form stable at
room temperature) and phase II (the low temperature form),
exhibit detail usually reserved for gases at low pressures.
In both phases the symmetry of ammonium ion has degenerated
from tetrahedral...
A method of calculating the normal vibrations of polymer molecules
is presented in detail. The method is based on that used by
Schachtschneider and Snyder in their analysis of polypropylene but
has not heretofore been published. The factoring of the infinite matrix
and reduction to the coordinates of the unit...
The velocity of sound in gases was measured, using an ultrasonic
wave train as a diffraction grating. The fundamental problems
involved in the optical technique are discussed. An apparatus utilizing
an objective lens of focal length 1.5 m and aperture f/20 was constructed
and used at an ultrasonic frequency close...
The ratio of the absolute infrared intensity, A₃/A₂, for the
parallel mode (2336 cm⁻¹) and the perpendicular mode (658 cm⁻¹)
of a nonpolar solute molecule, carbon dioxide, has been determined
in a nonpolar solvent, Nujol. The solution ratio (5.0) which has
been extrapolated to zero concentration is less than the...
Little is known regarding the catabolic mechanisms involved
in the breakdown of glucose in mung bean (Phaseolus aureus)
seedlings. Studies in other laboratories have shown that the TCA
cycle pathway is operative in mung bean leaves, and have demonstrated
the presence of enzymes for the oxidation of glucose to
glucuronic...
The infrared absorption spectrum from 3200 cm⁻¹ to 4025
cm⁻¹ of thin crystals of ⁶LiOH (99%⁶Li.) is presented and compared
to the spectrum of [superscript]NLiOH (93%⁷Li). A shift in only one of the band
pairs supports the lattice combinations model and assists in making
assignments for the major features of...
An analytical technique has been developed for the determination of methylmercury compounds in environmental samples. The technique is based on a two-stage procedure. In the first stage, methylmercury compounds are isolated from the sample matrix as methylmercury chloride (MeRgCl) by distillation. The distillation procedure is based on a series of...
Studies of anisotropic and isotropic Raman line shape yield information about the rotational motion (rotational correlation function) and non-reorientational (vibrational) lifetimes. The rotational motion of carbon disulfide has been studied previously by the techniques of Raman spectroscopy (6, 43), Rayleigh scattering (43, 46) and direct measurement (47). This work was...
In this report, three studies are presented that utilize computations to predict transformations, identities, and properties of environmental organic molecules. Each study shows how computations can lead to models of chemical behavior. The importance of this research is rooted in the need for understanding how human behavior and health intersect...
Xanthohumol [XN, (E)-6´-methoxy-3´-(3-methylbuten-2-yl)-2´,4´,4´´-trihydroxychalcone], the principal prenylated chalcone from hops, and its 2,3-dihydro- (DXN) and O6-desmethyl-2,3-dihydro- (DDXN) congeners, are of potential utility for the amelioration of metabolic syndrome; however, their complex bioactivity profiles cannot be properly studied and understood without access to appropriately produced synthetic materials.
In the first part of...
In this dissertation, excited state proton transfer (ESPT) and its inhibition in solution and protein environments are revealed using both femtosecond transient absorption (fs-TA) spectroscopy and femtosecond stimulated Raman spectroscopy (FSRS). Using a tunable Raman pump to enhance transient vibrational features of the photoacidic chromophore HPTS in methanol and methanol...