Fungi have long been used for discovery of new chemical scaffolds. In the clinical setting, the fungal natural products penicillin, statins, and cyclosporine have revolutionized medicine to treat diseases and infections. In the environment, fungal natural products have been used as herbicides, fungicides, and insecticides to protect crops, livestock, and...
The development of micro total analysis systems (µTAS), also called “lab-on-a-chip”, or microfluidic analysis systems, is presented in this dissertation. Various research areas, covering subjects from magnetic particles synthesis to novel microchip fabrication techniques, are explored to develop a lab-on-a-chip system capable of performing magnetic bead-based bioassays. These devices are...
Thermal analysis was used to investigate the following seven
systems: H₂S-B₂F₄, SOF₂-B₂F₄, COC1₂-B₂F₄, SF₄-B₂F₄, Xe-BF₃, NF₃-BF₃, and NF₃-BC1₃. In two of the seven systems
compound formation was observed.
In the system, H₂S-B₂F₄ the compounds H₂S[superscript .]B₂F₄ and
2H₂S[superscript .]B₂F₄ are formed. The compound H₂S[superscript .]B₂F₄ has a melting
point of...
Due to a number of disadvantages associated with the use of antibodies as
affinity stationary phases, researchers have recently began to explore the use of RNA
and DNA aptamers for use as affinity stationary phases. These molecules have been
shown to be a viable choice for applications in many methods...
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...
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...
Chlorinated aliphatic hydrocarbons (CAHs) such as vinyl chloride (VC) and 1,-2 dichioroethane (DCA), are wide-spread groundwater pollutants found at many contaminated field sites around the world. Quantitative tools are needed to determine the in situ rates of VC and DCA transformation to ethene in contaminated groundwater. The objective of this...
While properties are extremely important from an application point of view, it is crucial to have a detailed understanding of the underlying structural influence. Once a concrete correlation between the structure and the observed property is established, rational design of novel materials with optimized properties can be realized. These optimized...
The total synthesis of a highly potent cytotoxic marine natural product, phorboxazole A, is described. Both a palladium(II)-mediated and a palladium(II)-catalyzed intramolecular alkoxycarbonylation were used as key steps for the preparation of the two cis-2,6-disubstituted tetrahydropyran rings (C22-C26 and C11-C15) of phorboxazole A.
The synthesis used a convergent approach involving...
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)...
My work has focused on streamlining the study of organic compound structure, properties, and reactions by 1) understanding and using available computational software, 2) developing software packages to facilitate data manipulation as well as augment public programs, and 3) applying public and in-house developed software to further the understanding of...
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,...
Theoretical studies and experimental results are presented for the rotational motion of molecule's in crystalline solids. The group theory is solved for molecules of any symmetry matrix isolated at a site in a crystal field of any symmetry. As the potential terrier to rotation of the molecule relative to the...
Part I: Racemic and asymmetric syntheses of a new substance with prospective antidepressant properties were achieved. In vitro assays with synthetic racemates (±)-25 and (±)-26 suggested that the former is a relatively selective inhibitor of serotonin transporter whereas the latter is a more balanced inhibitor of both serotonin and norepinephrine...
2-Carboxy-3(3-cyclohexen-1-yl)propionic acid, 3-(3-cyclohexen-1-yl)propionic acid and 3-(3-cyclohexen-1-yl)propionyl chloride
were prepared in sequence from ethyl-2-carbethoxy-3-(3-cyclohexen-1-yl)propionate. Cyclization of 3-(3-cyclohexen-1-yl)propionic
acid in polyphosphoric acid resulted in the formation of 4, 5, 6, 7-tetrahydroindanone which was identified by its ultraviolet spectrum
and its physical properties.
7-Bicyclo[3.3.1] nonen-2-one was prepared by a Friedel-Crafts cyclization of 3-(3-cyclohexen-1-yl)-propionyl...
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...
Investigating the structure-property relationships of solid state materials can help improve many of the materials we use each day in life. It can also lead to the discovery of materials with interesting and unforeseen properties. In this work the structure property relationships of newly discovered layered oxypnictide phases are presented...
Studies toward the total synthesis of a highly potent cytotoxic marine natural product, phorboxazole A, were conducted and resulted in a route to an advanced intermediate, C4-C32, for this purpose. A key feature of our approach is the stereoselective synthesis of two cis-2,6-disubstituted tetrahydropyrans present in the macrolide portion of...
The solution chemistry and kinetic behavior of hafnium peroxy sulfate solutions ("HafSOx") is described in terms of peroxide content and solution speciation. Additionally, thin film behavior, including thermal behavior and solubility, is characterized, and a mechanism of patterning is presented, as well as parameters that should be considered when looking...
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 preparation and characterization of thin film oxides and chalcogenides by pulsed laser deposition (PLD) is presented. An overview of fundamental PLD concepts are presented and are followed by a description implementation and development of the PLD systems at OSU. We present the results of thin film growth of high...
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...
Mandelalide A has attracted considerable interest from the synthetic community due to its intriguing structure and important cytotoxic activity. Madeirolide A, a structurally related macrolide, shows promising antifungal activity but no appreciable anticancer activity. This dissertation describes synthetic studies toward mandelalide A, madeirolide A and their hybrid structures.
Part I...
Feeding of [3-¹³C, 2-¹⁵N]arginine, 38a, unequivocally established that the β-
arginine moiety of blasticidin S, 1, was formed from α-arginine by an intramolecular
migration of the α-amino group to the β- position. Further feedings using chirally
deuteriated arginines 38e and 38f revealed that the aminomutase process occurred with
inversion of...
An intramolecular variant of the modified-Julia olefination was demonstrated by the synthesis of α,β-unsaturated lactones in a mild and (Z)-selective fashion. The lynchpin reagent (benzothiazol-2-sulfonyl) acetic acid was synthesized in a straightforward fashion in 86% overall yield from commercially available 2-mercaptobenzothiazole via conversion to ethyl (benzothiazol-2-ylthio)acetate by base mediated alkylation...
The subject of this PhD thesis is part of a research domain of great present interest in new semiconductor materials for photovoltaic and thermoelectric applications. This domain contains the elaboration and the study of both Cu-based chalcogenides bulk and thin-film samples, driven by materials design principles.
One of the most...
Humanities have been craving more freedom and conveniences in whatever form. Carriages evolved to cars and ultimately to aircraft so that one can reach any place in the globe within a day. The mobile phone has enabled people to make a phone call without a need to find a phone...
Metal-oxo clusters are discrete, soluble pieces of bulk metal oxide. Cluster size, monodispersity, and chemical properties allow for potential use as solution-based precursors for functional metal oxide films. Classical monoalkyltin-oxo clusters are either charge neutral or stabilized by anions. The structure of Cs₄.₅H₂.₅[(BuSn)₃(α-SiW₉O₃₇)]*2H₂O enables its use in established ion exchange...
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...
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...
The first part of this manuscript is about the total synthesis of the Arundo donax bis(indole) natural products. The A. donax alkaloids were prepared using the first example of an ynindole Diels–Alder reaction. Each were then separated, isolated, and determined to have stable enantiomeric conformations at room temperature (Chen, J.;...
The continued long-term use of fossil fuels as a primary energy source has resulted in dramatic increases in greenhouse gas emissions and the associated concerns of climate change and environmental pollution. A key strategy to circumvent these issues is a global shift away from fossil fuels toward renewable energy sources....
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...
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...
This thesis presents basic studies, including structural, optical and transport measurements, on novel chalcogenide powders and single crystals. BiCuOSe crystals have been synthesized for the first time. The crystal structure of BiCuOSe has been refined and the optical band gap has been measured to be 0.83eV. Crystal structure refinements of...
Two approaches to the tricyclic core of the furanoeremophilane sesquiterpenoids are described. The first approach entails a projected Diels-Alder/retro Diels-Alder reaction of an acetylenic oxazole 64. Construction of the pivotal aldehyde 67 commenced from ketone 68. The acetyenic moiety was then introduced via a Felkin-Ahn addition of lithiopropyne to aldehyde...
Thermoelectric materials are playing a larger role in the global effort to
develop diverse, efficient, and sustainable energy technologies: primarily through
power-generating thermoelectric modules. The principal components of
thermoelectric modules are solid-state thermoelectric materials – typically heavily
doped semiconductors – that convert heat directly into electricity. However, this
conversion efficiency...
Electrochemical capacitors and batteries are two major electrochemical energy storage technologies, which have been investigated extensively to meet the rapidly-growing demand for higher energy, higher power, lower cost and enhanced safety in the past few decades. With the charge storage mechanism of electrostatic charge adsorption desorption via electrical double layers,...
The need for field and laboratory studies of the physical and
chemical behavior of environmentally significant organic molecules often
poses problems because of the toxicity of the chemical and the difficulty
of detecting it at environmentally significant concentrations.
Two dysprosium tracers, dysprosium (III) trisacetylacetonate trihydrate
and dysprosium(III) trisdibenzoylmethane monohydrate, were...
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...
Aminal radical intermediates were generated by the method of radical translocation and reacted in C-C bond forming reactions with electronically deficient alkenes (Schiedler et al. Org. Lett. 2012, 14, 6092). Aminal radical intermediates can participate in inter- and intra-molecular reactions using both Bu3SnH and (TMS)₃SiH as hydride donors. Carbon–carbon bonds...
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...
Studies toward synthesis of subunits of sanglifehrin A, an immunosuppressant featuring a highly substituted [5,5]-spirolactam moiety as well as a 22-membered macrocycle are described. The macrolactone contains a peptidic backbone characterized by an unusual [beta]-substituted (S)-piperazic acid and (S)-m-hydroxyphenylalanine units. These studies resulted in the synthesis of advanced intermediate 358...
In this dissertation, the structure and electronic properties of multiple metal oxide thin films are characterized and presented. Prompt inorganic condensation (PIC) of metal-oxo and –hydroxo clusters was evaluated as a technique for making metal oxide clusters in two separate studies. The first focuses on the synthesis of lithium niobate...
Ultrafast spectroscopy can exploit the structure-function relationship of chemical- and biological-based systems. More specifically, femtosecond stimulated Raman spectroscopy (FSRS) provides ground- and excited-state vibrational information with simultaneously high spectral (spatial) and temporal resolutions. The electronic counterpart, femtosecond transient absorption (fs-TA), complements FSRS data analysis as part of a comprehensive approach...
The increase in the demand for energy is estimated to be 28 TW by a year of 2050, which is twice of the energy produced in 2010, in response to the unprecedented growth of the global population. Current energy market is heavily relying on the fossil fuel, which brings the...
The first part of this thesis describes a study of the
characteristics of oxidation of a 1:2 iron(III):thiolate system in
methanolic solution and in water. This system was investigated as a
potential analog for the cysteine- and cysteamine-dioxygenase catalyzed
0₂-oxidation of cysteine and cysteamine, respectively, to the
corresponding sulfinic acids....
The enantioselective total synthesis of quinolizidine-containing natural product cermizine D and formal syntheses of senepodine G and cermizine C has been achieved. These natural products are members of the lycopodium alkaloids, which have attracted significant attention due to their exciting biological activities and the diverse structural scaffolds. Key steps in...
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...
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...
Grid-scale energy storage systems are urgently needed to increase the flexibility and rigidity of the grid for modern society and take full advantage of the renewable green energy resources such as solar energy and wind energy. Na-ion batteries (NIBs) and K-ion batteries (KIBs) have been emerged as one of the...
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...
Uranyl peroxide clusters are the newest family of polyoxometalates, discovered in 2015. Although this family is new, over 70 topologies have been reported. However, we lack the fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Here, we use a wide range of solution and solid-state characterization...
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...
Frontier research of non-aqueous actinide clusters is discussed. Since the inception of the uranyl peroxide clusters over the last decade, they have only been synthesized and characterized as solid crystals and in aqueous solution. This thesis provides thorough characterization of aqueous uranyl clusters and the first demonstration of uranyl cluster...
This thesis describes a study of the synthesis, stereochemistry,
and reactivity of cobalt(III) cysteinato (CyS) and related thiolato complexes.
The preparation of [Co(en)₂CyS]⁺ resulted in a product solution
containing a mixture of diastereomers in the ratio 2.3:1 (Δ:A). The isomers were separated by ion exchange chromatography, and
their absolute configurations...
The migration of chloride ions in concrete with steel reinforcement under cathodic protection was investigated. Mortar blocks (15 cm x 15 cm x 17 cm) of various composition (water to cement ratio, chloride ion content) were cast with an iron mesh cathode embedded along one face and a thermally sprayed...
Porous carbon is indispensable in modern technology applications. It is used for energy storage, gas separation, water purification, catalyst support, and chromatography. The diversity of its applications stems from its unique properties, including high specific surface area, tunable pore volume, and chemical stability. Specifically, the large surface area provides high...
State-of-the-art, high-resolution mass spectrometry techniques for acquisition of metabolomic and lipidomic data coupled with advanced computational methods provide new opportunities for interpreting large and complex datasets and comprehending the underlying biological processes of diseases. Both metabolomics and lipidomics strive to obtain comprehensive analyses of small molecules, i.e., metabolites and lipids,...
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...
The tosylhydrazones of 2-heptanone, 4,4-dimethy1-2-
heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2-
one were synthesized and decomposed under a variety of
reaction conditions: dry lithium and sodium salt pyrolyses,
sodium methoxide thermolyses in diglyme and photolyses of
the lithium salt in tetrahydrofuran. The saturated analogues
2-heptanone tosylhydrazone and its 4,4-dimethyl
isomer afforded the...
Put generally, the work I have conducted in my time at Oregon State University has been to answer two questions. The first of these is “Why do I get this particular product from this particular chemical reaction?” and the second is “How do the reagents in this chemical reaction lead...