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...
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...
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...
The primary focus of this work is on examining structure-property relationships of interest for high-power nonlinear optical and laser crystals. An intuitive and simply illustrated method for assessing the nonlinear optical potential of structurally characterized noncentrosymmetric materials is introduced. This method is applied to materials including common quartz and tourmaline...
An expedient approach to the synthesis of a wide range of highly programmable biaryl templates has been accomplished. Utilizing the Diels-Alder [4+2] cycloaddition, a wide range of tri- and tetra-ortho-substituted biaryls have been synthesized in only three to four steps from commercially available materials. We have successfully synthesized entire classes...
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...
An oscillating plasma glow discharge detector for gas
chromatography is used to obtain fingerprint information
about an analyte by combining both the average cell
current and oscillation frequency signals. Five homologs
each of the n-alkanes, 1-alkenes, 1-alkynes, 2-ketones and
aldehydes are studied. Although triplicate determinations
had some scatter due to...
A new general method is developed for the optimization of
HPLC ternary or pseudo-quaternary mobile phases which are
represented by the trilinear coordinate system. This method can
predict the global optimum of the mobile phase composition. The
global optimum composition along each edge of the triangle and
the corresponding selectivity...
An atmospheric pressure argon glow discharge is shown
to detect trace levels of carbohydrates in aqueous flowing
systems, using either of two glow discharge solution
interface configurations. The first configuration consists
of an oscillating glow discharge sustained between a flowing
aqueous cathode and platinum anode. Picomole and micromolar
mass and...
The use of an adjacency matrix to determine distant (not maximal or
minimal) subgroup and supergroup relationships between crystallographic spacegroup
types is described. Full lists of space-group types that are supergroups and
subgroups for every space-group type were compiled. A list of the space-group
types connected to each space-group type...
The development of microfluidic devices for heavy metal extraction is presented in this dissertation. Various research areas, covering subjects from photochromic compound syntheses to microchip fabrication techniques are explored to develop microfluidic devices capable of extracting heavy metal ions from drinking water. Through integration of the beneficial characteristics of both...
Aromatic heterocycles are core structural motifs in natural products, pharmaceuticals and biological polymers. Indoles, in particular, represent a significant subclass of aromatic heterocycles, both in terms of sheer numbers, but also in biological and pharmaceutical relevance. As such, new methodologies for the synthesis of indoles represent an important and continually...
The spectrophone method for the study of vibrational relaxation
has been claimed to possess a distinct advantage over the more commonly
used ultrasonic techniques in that it permits the relaxation of
the various infrared-active vibrational modes in a polyatomic molecule
to be studied separately. A discussion of the rate equations...
The emphasis of this work has been in two areas of optical materials - the
crystal-chemical development of new optical frequency converters and the synthesis
and study of new hosts for Cr³⁺ luminescence and lasing.
A simple method has been developed to identify promising frequency-doubling
materials containing triangular oxoanions by...
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...
Ultraviolet spectroscopic methods for the determination
of dissociation constants can only be applied to
those compounds having protonatable sites conjugated with
or inherent in a chromophoric group of the compound.
The determination of the dissociation constants of
organic nitrogeneous bases by ultraviolet spectroscopic
methods was found to be only reliable...
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 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....
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....
Studies were carried out to determine the absolute stereochemistry of
botryococcene (1). The natural product was degraded to two sets of 'y- and 8-
valerolactones. All enantiomeric variations of these lactones were synthesized in
optically pure form starting from (S)- and (R)-methyloxiranes. 1H NMR correlation of
natural and synthetic materials...
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...
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...
Mass Spectrometry has emerged as an analytical core technique in omics sciences, in particularly mass spectrometry has advanced the fields of proteomics, metabolomics and lipidomics in recent years. Mass spectrometric techniques have enabled the characterization and determination of abundance levels of a wide range of biomolecules at molecular and system-wide...
A synthetic approach toward the two major fragments of cathedulin K-19,
euonyminol (4) and dimethyl cathate (69), was investigated. Synthesis of
dimethyl cathate was accomplished in 3 steps starting from 73. Efforts directed
towards the synthesis of euonyminol, a highly oxygenated dihydroagarofuran
sesquiterpene, was advanced to a stage in which...
The reactions of EGTA, [ethylene bis (oxyethylenenitrilo)]
tetraacetic acid, with 51 metal ions have been studied spectrophotometrically in aqueous solutions.
The absorption spectra of the
chelates formed were measured with a recording spectrophotometer
between 200 and 700 mμ. The pH of each solution was varied and a
spectrum was scanned...
Solubility studies on the heavy metal sulfides in liquid hydrogen
sulfide at room temperature were carried out using the isopiestic
method. The results were compared with earlier work and with a
theoretical result based on Raoult's Law. A relative order for the
solubilities of sulfur and the sulfides of tin,...
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...
A heat stable derivative of bovine serum albumin containing
300 residues of glycine added to 30 sites on the surface of the protein
has been prepared. This derivative may be heated to 100° C for
prolonged periods of time without aggregation. By comparison,
native BSA aggregates at 62° C under...
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...
This thesis is concerned with the development and use of routine
analysis techniques based on chemiluminescence (CL) detection for: 1)
ethanol in gin down to the 0.3% (v/v) level; 2) the antioxidants propyl
gallate and BHA in lard to levels as low as 0.3 and 0.2 mg/L, respectively; 3) pyrogallol...
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 development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging...
The microbial communities play a crucial role in maintaining human health and cause diseases through very complex microbial chemical interactions. Therefore, these microbial communities have drawn much attention to the scientific communities. To elucidate these complex microbial communities and the chemical interactions within it, one or more isolated species of...
My work has focused on using density functional theory to elucidate mechanisms of organocatalytic and transition metal catalyzed reactions by considering competing mechanisms. In each of the three presented studies computational investigation complemented experimental work by predicting stereoselectivity or revealing origins of stereo, regio, or chemoselectivity.
A study on the...
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...
A variety of laser spectroscopic methods are employed in this
thesis research for studies of CF₃NO, an interesting model
photodissociative system, and for investigation of low energy rotations
and vibrations of small molecules and low molecular weight clusters in
free jet expansions.
Nonradiative energy decay for electronically excited CF₃NO is...
AT-cut piezoelectric quartz crystals coated with low vapor
pressure materials are evaluated as digital transducers in completely
digital detection systems for monitoring gas streams. Mathematical
relations describing the detectors are developed and tested. Specific
application is made to monitoring gaseous sulfur compounds commonly
found in stack effluents of pulp mills....
The development of a least squares model for the
determination of compliance constants from various combinations
of vibration frequency, mean square amplitudes
of vibration and centrifugal distortion data is discussed.
The resultant model is applied to frequency and mean square
amplitude data for NO₂ and N₂O₄ and to frequency and...
Several approaches to the synthesis of methymycin were
investigated. Segment A (39), containing functionality corresponding
to C-9, 10, and 11 of methynolide was made in
six steps from propionaldehyde in an overall yield of 37%.
Oxidation of 34 with silver nitrate gave 35 which, upon hydroxylation
with hydrogen peroxide, gave...
Several approaches to the synthesis of penicillin from 2-iminothioazolidine
50, from 2-thiothiazolidine 66 and by photocyclization of
77 and 78 were investigated. 2-Iminothiazolidine 50 was prepared
from dibromoester 45 by the action of benzylamine followed by treatment
of aziridine 46 with potassium or ammonium thiocyanate. Attempted
introduction of a two-carbon...
An approach to the generation of polyketides was investigated,
which involved ozonolysis of 6, 7 cyclopenteno -1> 4, 5, 8 -tetrahydromethoxy-
3-methylnaphthalene (26), to produce what is believed to be
polyketide 27. Compound 26 was formed by the following sequence:
Die ls -Alder addition of 1, 2 -dim.ethylenecyclopentane and 2...
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...