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...
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,...
Tuberculosis (TB) is a pressing global health issue with approximately one third of the world’s population infected by this bacterium. As one of the most dangerous infectious diseases, it has killed approximately 1.7 million people of all ages around the world per year (World Health Organization, 2016). Currently, several drugs...
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...
The design, construction and operation of a fluorometric reaction
rate instrument is described. The instrument is designed for simple
operation with maximum versatility. Advantages and modes of
operation of the system are discussed in detail. The instrument is
used for the kinetics-based determination of trace levels of Ag and Al....
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...
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...
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...
Linear alkylbenzenesulfonate (LAS) is the most widely used anionic surfactant in
commercial detergent formulations. The environmental fate of LAS is of interest because
of its disposal to wastewater treatment facilities and subsequent occurrence as a
micropollutant in surface waters and groundwater. While LAS fate in wastewater
treatment systems and surface...
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 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...
Irradiation of a tryptamine linked through its side-chain nitrogen to an alkylidene malonate residue results in an intramolecular [2 + 2] cycloaddition to the indole 2,3-double bond. The resultant cyclobutane undergoes spontaneous retro-Mannich fission to produce a spiro[indoline-3,3-pyrrolenine] with relative configuration defined by the orientation of substituents in the transient...
Three distinct methods to achieve the stereoselective synthesis of carbon-carbon bonds were investigated, encompassing: (i) the formation of axially chiral biaryl molecules by enantioselective Suzuki cross-coupling, (ii) the synthesis of α-phenylalkylboronic esters by enantioselective chain extension, and (iii) the stereospecific synthesis of alkenes by eliminative cross-coupling of enantioenriched sp³-hybridized carbenoids....
In previous work (Blakemore et al. Org. Lett. 2005, 7, 4721; Heterocycles 2006, 70, 609), successful elaborations of the lupine alkaloids (±)-α-isosparteine (dl-2) and (±)-β-isosparteine (dl-3) were realized from a common tetraoxobispidine precursor, 3,7-diallyl -2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (93). Herein, the tetraoxobispidine approach to lupine alkaloids was extended to a total synthesis of...
A Diels-Alder approach to biaryls (DAB) has been applied towards the synthesis
of highly substituted, programmable biaryl templates. Tri- and tetra-ortho-substituted
biaryls can be produced in just three to four steps from commercially available materials
utilizing the Diels-Alder [4+2] cycloaddition. The methods described herein will
illustrate the ability of mono...
The intriguing size- and shape dependent properties of nanoparticles have garnered recent attention in many science and engineering areas. When the particle size is in the nanometer size range, the material exhibits very different properties such as surface plasmon resonance (of gold nanoparticles) and superparamagnetism (of iron oxide nanoparticles). The...
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...
Ultraviolet spectroscopy and dispersive solubility parameters
correlated to the ratios of retention times have proven valuable in
classification of gas chromatography stationary phases by the donor-acceptor
properties. Iodine was directly dissolved into stationary
phases and the absorption frequency shift of complexes was correlated
with the carbon tetrachloride/chloroform retention ratio on...
This dissertation presents a study of structure-property relationships within 3d/4d metal oxides containing precious metals through detailed structure refinements using high-resolution neutron and X-ray diffraction data along with exploration of the resultant properties.
Oxides of 4d or 5d transition metals tend to show new topological phases due to significant spin-orbit...
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...
This study identified new compounds with pest control activities. The two sources of candidates that were followed here were the main heartwood extract of Alaska Yellow Cedar (AYC) constituents and several semi-synthetic counterparts. Five compounds were isolated and identified for the first time in AYC heartwood in this research: two...
The discovery of new blue pigments is a field of great interest, as commercially available pigments present properties that make them undesirable such as poor sustainability, cost, and stability. By researching solid solutions with the melilite structure, we discovered a new solid solution Sr2Zn1-xNixGe2O7, with 0.1 ≤ x ≤ 0.6,...
The structural architecture present in marine toxin azaspiracid - 20 stereocenters, 9 rings, 3 separated spirocenters - has attracted considerable synthetic attention. Our efforts toward the synthesis of azaspiracid have led to the completion of both C₁-C₂₆ northern and C₂₇-C₄₀ southern halves. Herein, the
synthesis of southern FGHI ring system...
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...
Traditional approaches for the direct preparation of alkenes are unable to fully control either the stereochemical configuration of the carbon-carbon double bond or else the regiochemistry of the substituents surrounding it. The recently introduced concept of carbenoid eliminative cross-coupling (CEXC) offers a remedy to these deficiencies by providing for a...
The work presented here is the culmination of efforts in describing complex chemical systems with statistical methods, thereby providing relatively simple quantitative models and easily comprehensible qualitative insights. The following investigations have various goals, such as development of new methods, fundamental understanding, molecular control of chemical species, and advancement of...
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...
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...
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...
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...
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Figure 2.28. The 1st cycle GCD profiles of a Cu||AC full cell performance with the
N/P ratio of
As scientists, we have an affinity for order: repeating crystal structures, Euclidean space, continuous functions… Even concepts such as defects are discussed in the context of distracting from order. Things are most logical and best described in straightforward, taxonomical fashion. But what happens when the very application desired is dependent...
Exploratory synthesis plays an important role in the quest to discover new materials. There are very few structurally characterized alkali metal containing bismuth vanadates. Hybridization of the 6s and 6p orbitals of Bi[superscript 3+] and the resulting lone electron pair yields some very interesting stereochemistry and steric related properties. Some...
The rate of the C¹⁴0₂ release from glucose, specifically labeled
with C¹⁴ at 1, 2, 3+4, and positions, was used to study the relative
participation of pathways of glucose catabolism in red beet slices.
Evidence was obtained which indicated that in mature red beets glucose
was catabolized mainly via glycolysis-tricarboxylic...
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 study of the obstructive factor by Hawkes (11) showed a relation
between the obstructive factor and velocity using a continuous
method. Later, Bowers and Hawkes (12) developed a similar method with
some improvements in the apparatus and found out that the obstructive
factor was not flow dependent. This study...
Gas-solid chromatography often has asymmetrical elution
peaks. This is attributed to nonlinear isotherms, multi-energy
adsorption sites, and slow processes. This study utilized a stopflow
gas chromatograph with various NaOH and NaCl modified
aluminas as adsorbents and methane as adsorbate to determine the
influence of surface area and pore volume distribution...
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...