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...
Polyhalogenated benzenes have been analyzed by standard electron capture
chemical ionization mass spectrometry (ECCI/MS), and electron monochromator mass
spectrometer (EM/MS) systems. The EM/MS experiments distinguished electronegative
compounds (especially isomers) by transient negative ions (TNIs) of the same mass but
differing energies and/or the formation of distinct TNIs of different masses...
Benzylsuccinate (BSA), methylbenzylsuccinate (methylBSA), and ethylbenzylsuccinate (ethylBSA) are unambiguous anaerobic biotransformation products from toluene, xylenes, and ethylbenzene decay, respectively, and may be used to indicate intrinsic bioremediation is occurring at hydrocarbon-contaminated sites. In order to improve upon current methods that detect and quantify anaerobic hydrocarbon metabolites in field samples, solid-phase-extraction...
The chemistry of hafnium oxide based and materials are described in the context of ion exchange and lithography. HafSOx, represented by the composition HfO₂₋[subscript x](SO₄)x, is described to possess a significant capacity towards ion exchange in acidic and basic solutions, enabling films of HafSOx to be cleanly and readily be...
Public attention and concern about per- and polyfluoroalkyl substances (PFASs) are increasing due to detection of PFASs in drinking water supplies, the environment, including remote locations, and wildlife and to the lowering of the federal health advisory levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in drinking water. Aqueous film-forming...
Oxide materials exhibit a wide variety of structures and properties. In particular, transition metal oxides tend to be highly stable while exhibiting a wide range of properties that can be used for numerous applications. This work focuses on investigating how the structures’ of 4d and 5d transition metal oxides influences...
Crystals of an incongruent-melting compound, Ba₃MgSi₂O₈, were grown by the flux method and its structure was determined by single crystal X-ray diffraction methods. Ba₃MgSi₂O₈ crystallizes in trigonal space group P-3[bar]m1 with a = 5.6123(3) Å, c = 7.2667(9) Å and Z = 1. Eu²⁺ ions prefer one crystallographic Ba site...
The materials Fe₂(Si,Ge)(S,Se)₄, Cu₃PS[subscript 4-x]Se[subscript x] (0 ≤ x ≤ 4), and Cu₃PxAs[subscript 1-x]S₄ (0 ≤ x ≤ 1) have been synthesized and studied as new earth-abundant absorbers for single and multijunction photovoltaic cells as well as solar fuel generation. The synthesis, single-crystal growth, and optical and electrical properties of...
The silicate phases of 11 pallasites were analyzed instrumentally
to determine the concentrations of some major, minor, and
trace elements. The silicate phases were found to contain about
98% olivine with 1 to 2% accessory minerals such as lawrencite,
schreibersite, troilite, chromite, and farringtonite present. The
trace element concentrations, except...
This dissertation outlines two approaches for improving the efficiency and reducing the cost of photovoltaic energy generation. First, the structures of known binary copper and iron compounds are used to choose the promising compositions Fe₂XS₄ (X = Si, Ge), Cu₃TaQ₄ (Q = Se, Te), and BaCuQ'F (Q' = S, Se,...
The rate of removal of benzene, toluene, ethylbenzene and the xylene isomers (BTEX) from contaminated groundwater is needed to design remediation processes. Benzylsuccinic acid (BSA) and methyl-benzylsuccinic acid (methyl BSA) are unambiguous metabolites of anaerobic BTEX biodegradation. An analytical method for quantitative determination of BSA in groundwater samples was developed....
Phosphate and peroxide stabilize new oxo-hydroxo niobium clusters in water at low pH. The clusters open a new chapter in aqueous niobium chemistry under acidic conditions. The clusters also produce atomically smooth, amorphous niobium oxide phosphate (NbPOx) thin films. Reaction pathways from cluster solutions to amorphous niobium oxide phosphate solids...
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...
Solid state luminescent sulfides are prepared as powders in order to elucidate the relationship between structure and light emission. While the sulfides studied in this dissertation are known phosphors, materials are investigated in a variety of new ways. Elementary properties and structures of MgS are reviewed, and preparation of MgS...
In this dissertation, the spectroscopic properties and thermodynamic stability of a class of materials known as metal oxo and hydroxo clusters are studied. In aqueous solutions, many metals can aggregate into discrete clusters of metals bridged by oxo or hydroxo ligands. These clusters are of particular interest to us for...
The work presented here is focused on applying basic principles of solid-state chemistry to the study and development of new wide band-gap semiconductors and insulators for photovoltaic and electronic-device applications. Analysis of crystal structure, band structure, optical band gap, morphology and transport properties provides fundamental insight into materials performance as...
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)...
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,...
The preparation of holocellulose accurately and rapidly is very
important to study the nature and relationships of the carbohydrate
components and the substituent groups, acetyl, carboxyl, and methoxyl.
In as much as bromine was thought to be less destructive to
wood than chlorine, it was decided to attempt to isolate...
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 Disney Princesses are some of the most beloved and well-recognized characters in animation across the globe. Most of these characters sing throughout their movie. This essay analyzes what I refer to as the “I Want” song of several Disney Princesses. It is divided into three sections, one for each...
A large-scale preparative method for potassium di-n-butylborate
in triethylamine solvent has been developed. The reaction of
potassium di-n-butylborate I with trifluoromethyl iodide has been
shown to yield trifluoromethyl di-n-butylborane and other products.
Reaction of this substance with boron trifluoride gave trifluoromethyl
boron difluoride. Reactions of diboron tetrafluoride, boron tribromide,
and...
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...
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 design and construction of two new sample injection systems or nozzles, for use with the Oregon State electron diffraction apparatus are discussed. One of these nozzles was intended for use with volatile samples the vapors of which were to be heated or cooled over the range -196 to 540°C;...
The synthesis of axially chiral polyfunctional derivatives of 8,8'-biquinolyl was explored and the catalytic action of appropriate derivative types investigated in three separate processes: (1) the silylcyanation of carbonyl groups and imines, (2) alkylation of a glycine Schiff-base via phase transfer-catalysis, and (3) direct amide bond formation from simple amines...
Voltage scanning coulometry was used to study the effects of
electrode surfaces and metals on the electrochemistry of the ferric-ferrous couple and the silver ion-silver metal couple. The analytical
technique called voltage scanning coulometry is very similar to controlled
potential coulometry. The main difference is that in voltage
scanning coulometry...
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...
There has been a tremendous growth in interest in carbon nanodots (C-dots) in the past several years. As a nascent nanomaterial, C-dots have shown great promise in applications that benefit from their superior water dispersibility, low toxicity, non-blinking fluorescent output, chemical and biological compatibility, ease of functionalization and resistance to...
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...
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....
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...
Automation of computational chemistry, while only an engineering feat, has the potential to accelerating computational research be removing all by the science. The work in this thesis mainly discusses fundamental understanding of complex chemical systems. What is not obvious are the numerous tasks necessary for this fundamental understanding. Under the...