Production of 89Zr serves as a crucial preliminary step for exploring Zr-chelates, determining their stability constants, and advancing radiolabeling methodologies for monoclonal antibody based theranostics. 89Zr is typically produced by the irradiation of natural yttrium targets, a process extensively documented in scientific literature. Two primary methods are employed: the 89Y(p,n)89Zr...
Nanoparticles are a hugely diverse category of material that have a wide variety of biomedical applications, and developing tools for biological research with high cellular uptake is critical to their effective application. However, rarely is attention paid to the exact mechanism by which this is occurring, with most studies focusing...
Metabolomics has recently gained momentum in biomolecule research and complements the genomics and proteomics research space. Metabolomics strives to detect, identify, and quantify all metabolites present in biological samples. In particular, biomolecular analysis using ultra-performance liquid chromatography combined with mass spectrometry (UPLC-MS) has become increasingly important for metabolomic analyses. Similarly,...
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....
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 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...
The design of a novel Tabletop Role Playing Game was conducted with the aim to create a game system that provides both rigid rules and more creative outlets compared to existing games. The project focused on player-developed mystical abilities known as Spells, whereby the rule of the game guides the...
Capstone 1157 is a commercial reference material used in aqueous film forming foam (AFFF) applications and was manufactured by DuPont. The material’s purpose in this project was to be the sole carbon source to microbes in a biodegradation study in a microcosm environment. The goal of this project was to...
The concept of reducing laboratory operations into microfluidic devices has been an attractive area of research for several decades. Due to several advantages of porous-media microfluidic devices including low mass, portability, power-free fluid transport, and the ability to store dried reagents in the porous structures, these devices show great promise...
Per- and polyfluoroalkyl substances (PFAS) are a group of anthropogenic compounds that are used ubiquitously in different industrial fields. However, concerns regarding the potential health impacts of PFAS, including perfluoroalkyl carboxylic acids
(PFCAs) and perfluoroalkyl sulfonates (PFSAs), has raised stakeholder interest regarding continued use of PFAS. Analytical methods for PFAS...
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...
Radiation exposure to the brain can occur from a variety of events, including space missions, nuclear accidents, and clinical treatments. The effects of high dose radiation are well studied, but those of lower dosage are more elusive. Decline of memory and cognition is observed in patients exposed to low dose...
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...
The first part of this manuscript is about the total synthesis of the aspidosperma alkaloids leuconoxine, melodinine E and mersicarpine. Our synthetic strategy used a radical translocation-conjugate addition cascade to construct the core of the natural product. Specifically, a vinyl radical was generated from the homolysis of the C–I bond...
The bimolecular reaction of two carbenoid species resulting in the formation of a carbon-carbon double bond (pi-system), referred to herein as carbenoid eliminative cross-coupling (CEXC), involves a series of three fundamental steps: (i) ate-complex formation (transmetalation), (ii) 1,2-metalate rearrangement, and (iii) beta-elimination. All three steps are stereospecific and so the...
Ultrafast spectroscopy has recently gained momentum as a powerful, noninvasive characterization toolset capable of studying a diverse array of samples with applications in chemistry, physics, biology, engineering, and more. Two popular ultrafast spectroscopic techniques include femtosecond transient absorption (fs-TA) and femtosecond stimulated Raman spectroscopy (FSRS). The latter of these techniques...
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...
Metal-oxo clusters can be described as soluble pieces of metal-oxide frameworks. Metal-oxo clusters are also the building blocks for the Metal-Organic Frameworks (MOFs) and coordination polymers. A better knowledge of metal-oxo clusters helps fundamentally understand geosciences, molecular engineering, catalysis, single-molecule magnetism, and MOFs for synthesis, design, and modification of these...
In Dual-ion Batteries, anions as charge carriers might be a potential technique of energy storage. While fluoride anion has been selected as a promising charge carrier for energy storage due to its high charge/mass ratio and small ionic radius, carbonate anion has never been reported as a charge carrier for...
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...
The general theme of this dissertation is the development of new analytical sensors to quantitatively study biological and environmental samples in aqueous and non-aqueous environments. A platinum ultramicroelectrode (UME) and a unique carbon-based pH microprobe were used to design a new SECM-based electrochemical bioassay. The Pt UME was used to...
With Alzheimer’s disease being the most prominent form of dementia, finding potential treatments for the disease is imperative. This study explored the non-steroidal anti-inflammatory drug ibuprofen as a potential treatment to normalize the hyperactive N-methyl-d-aspartate receptor (NMDAR) within the 5xFAD mice early in the disease pathology before cognitive decline. Female...
When the Affordable Care Act was passed in 2010, eligibility for Medicaid was expanded to include people whose income was less than 138% of the federal poverty level. In 2012, the Supreme Court ruled that states could choose whether to expand their Medicaid programs or not. The objective of this...
The interface between a biofilm and the underlying substrate to which it is attached is challenging to study. Currently, available methods of studying this microenvironment have not been able to record data in real-time over a time period in the range of days. To address this challenge, we report the...
In this dissertation, I present experimental observations of multiply charged atomic ions (MCAI) generated from interactions of atomic/molecular clusters with moderately intense nanosecond laser pulses. This process is also known as Coulomb explosion (CE) and it has been extensively studied in intense laser fields using ultrashort pulses. Several prevailing theories...
Polyoxometalates (POMs) are anions consisting of three or more early transition metals ™ (Gr V and VI) oxoanions (in their highest oxidation state) linked together by a shared oxygen bond to form a 3D framework. Polyoxometalates (POMs) are a rapidly growing class of metal oxo clusters with a wide range...
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 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 presence of per- and polyfluoroalkyl substances (PFAS), organic contaminants first synthesized in the 1940s, has been reported worldwide in a variety of environmental matrices and ultimately in biological systems including humans. Ongoing research into PFAS has included identifying novel PFAS, assessing their fate and transport in the environment, and...
Substituted phenols are important substructures for pharmaceuticals, agrochemicals, natural products and biological probe molecules. The properties of phenolic molecules are substantially influenced by the substitution patterns of the phenolic ring. The chemical synthesis of phenols with various substitution patterns is an enduring challenge and multiple strategies have emerged. However, some...
A molecular approach to metal oxides allows to the study to fundamental bonding and formation behavior for such metals. Moreover, the molecular nature of such oxides or metal-oxo clusters allows the possibility of exploitation of the properties of the parent oxides. The tetravalent metals, in specific, (M=Zr, Hf, Ce, Th,...
In this dissertation, I describe the experimental investigation of electron diffraction of neutral and ionic clusters doped into superfluid helium droplets. The project is aimed at contributing to the development of an overall approach called ‘serial single molecule electron diffraction imaging (ss-EDI), a potential approach to solve macromolecule structures bypassing...
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 grand plan of carbon neutralization and COP26 in Glasgow require a quick shift of energy sources from conventional fossil fuel to a more renewable substitute such as wind, or solar energy. However, the intermittency of those renewable energy sources does not meet the demand of the energy, which requires...
The unique capability of carbon-based ion-selective electrode (ISE) to perform highly sensitive anodic stripping voltammetry, while maintaining all the properties of an ISE, is demonstrated in terms of sensitivity, detection limit, response time and selectivity. Square wave anodic stripping voltammetry involves deposition and dissolution steps of metal ions, which means...
Pseudomonas fluorescens NZI7 was first isolated from a New Zealand mushroom farm in 2001. This Gram-negative bacteria can cause brown blotch disease in the basidiomycete mushroom Agaricus bisporus. P. fluorescens NZI7 can also repel grazing by the nematode Caenorhabditis elegans, a natural predator of P. fluorescens NZI7. Potentially implicated in...
Chalaniline A, an unusual xanthone-like aminofulvene with modest cytotoxicity, and chalaniline B [1-anilino-2,8-dihydroxy-3-(hydroxymethyl)xanthone], an antibacterial aminoxanthone, were previously isolated by Loesgen and coworkers from vorinostat-treated Chalara sp. 6661. Of note, the anilino moiety found within both chalaniline structures originates from biotransformation of the HDAC inhibitor vorinostat (SAHA, suberanilohydroxamic acid) by...
The demand for the development of sustainable energy is an all time high as we burn through limited fossil fuel reserves and as environmental concerns rise every year. Renewable energy sources such as wind and solar power have limitations due to inconsistent power supply that cannot meet the regular needs...
Per- and polyfluoroalkyl substances (PFAS) are a group of contaminants of great concern due to their toxicity and ubiquity in the environment. Remediation efforts historically have focused on granular activated carbon (GAC) because of its low maintenance and relatively low cost. However, GAC is not PFAS selective and is especially...
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...
In this dissertation, a novel method for analyzing computed transition states (TS) for organic reactions is disclosed. It introduces the use of localization-delocalization matrices as parameters in a linear free energy relationship to determine the transition state interactions responsible for differences in energy between the major and minor TS in...
Naturally occurring assemblies, such as DNA and proteins, utilize intermolecular forces (i.e H-bonding and van der Waals) to assemble. Utilizing these electrostatic interactions has only just started in the past five decades to be a tool used in synthetic chemistry in what is known as supramolecular chemistry. Supramolecular chemistry has...
Metabolomics and lipidomics lay the foundation of personalized medicine. The technological advancements in mass spectrometry techniques in combination with computational algorithms and methods have enabled the study of small molecules (metabolites and lipids) for understanding the disease state and biological pathways, the identification of biomarkers and the generation of predictive...
Photoactivated biomedical tools like fluorescent biosensors and optogenetic proteins have increased in popularity due to the precision targeting and activation used for in vivo applications. In nature, the initially discovered parent proteins exhibit properties such as fluorescence quantum yield (FQY), fluorescence color, and photoswitching dynamics that are unfavorable in mammalian...
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...
Nitrate (NO₃-) accumulation in water sources is a serious health and environmental concern. Common methods used to reduce NO₃- accumulation have one or more undesirable traits that limit their efficacy in large-scale decontamination. However, treatment of NO₃- electrochemically is a promising area of study because of the absence of toxic...
Oxylipins are a class of bioactive lipid metabolites derived from polyunsaturated fatty acids (PUFAs) via enzymatic and non-enzymatic pathways. In order to elucidate their overall biological effects, the knowledge of the entire oxylipin profile is needed as oxylipins can have similar or opposing effects in regard to inflammatory events. Their...
Toxoflavin, a toxic secondary metabolite produced by a variety of bacteria, has been implicated as a causative agent in food poisoning and a virulence factor in phytopathogenic bacteria. This toxin is produced by the tox operon in Burkholderia glumae, in which the encoded protein, ToxD, was previously characterized as essential...
Global interest in reducing carbon emissions by use of alternative energy sources makes nuclear energy production and the impacts of the nuclear energy cycle relevant. Studying the aqueous speciation of tetravalent metals commonly used for nuclear energy (uranium, thorium, plutonium) can inform us of general metal properties and their behavior...
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...
A simple Janus-type membrane-based wicking microfluidic device fabricated on a polycaprolactone-filled glass microfiber membrane enables separation and collection of blood plasma or serum from whole blood. This device bridges the wicking and cut-capillary-based solution transport mechanisms in a single membrane. The initial portion of the device is fabricated using selective...
The total kinetic energy (TKE) in the fast neutron induced fission of 237Np was measured for neutron energies from En = 2.6 – 45.7 MeV at the LANSCE- WNR facility. The postTKE release decreases non-linearly with increasing incident neutron energy and can be represented as TKE(MeV) = (169.365 ± 1.551)...
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...
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...
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...
In this report, two studies are presented that utilize computations to predict and elucidate the reaction mechanisms of two different copper catalyzed reactions. Each study provides insight into the various chemical transformations, as well as the how and why behind regioselectivity and isotopic selectivity. The importance of this research is...
In the past decades, femtosecond stimulated Raman spectroscopy (FSRS) has been gaining tremendous popularity in fundamental sciences stemming from chemistry to biology. It is capable of capturing both equilibrium and non-equilibrium structural information across a broad range of timescales with simultaneously high temporal and spectral resolutions. Femtosecond transient absorption spectroscopy...
In the 21st century, environmental deterioration is now an indisputable fact. Reliable and economically viable electricity systems based on renewable sources are urgently needed to replace the environmentally detrimental fossil fuels. The feasibility of incorporating renewable-but-intermittent solar and wind energy heavily depends on the development of cost-effective and safe technologies,...
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...
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...
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...
Novel graphite intercalation compounds (GICs) and associated chemistry have been explored, specifically: (1) containing alkyl- substituted imidazolium cations; (2) a series containing alkaline earth metal (Mg, Ca, Sr, Ba) cations with ethylenediamine (en) co-intercalates; (3) showing reversible intragallery M-M bonding and (4) via electrochemical intercalation of Mg cations with potential...
This work investigates the relationship between the local structure and physical properties of a set of classical (MgTiO3, CaTiO3, SrTiO3, and BaTiO3) and complex ((1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3[BZT-BCT], Na0.5Bi0.5TiO3 [NBT]) perovskite electroceramics. The materials in this work were synthesized via standard solid state ceramic synthesis, the structure was investigated through a number of...
Nowadays selective separation processes are sought after more than ever before. They are indispensable to meet the growing demand for individual rare earth elements, minor actinides partitioned from fission-produced lanthanides, as well as, overall, more concentrated and high-purity products. This research focuses on such separation techniques as solvent extraction which...
An emerging strategy to reducing food waste is converting food processing byproducts to nutritious and inexpensive food ingredients. A relevant food processing waste stream is brewers’ spent grain (BSG), the primary byproduct of beer production. BSG is a promising candidate as a food ingredient because of its high protein and...
The purpose of this study was to analyze the scores of a mental math quiz taken by the CH 231 trailer course at Oregon State University and to determine courses of action to increase the success of students in general chemistry based on the results of the analysis. Students were...
The study of natural products (NPs) and their application has shaped humanity. Starting with the idea of using plants as medicine, it has now grown into the science of purifying and identifying organic molecules from nature to study their inherent biological activities. Understanding the molecular structures of NPs is the...
Understanding structural evolution in solids as composition changes is essential to materials properties prediction. Such structure-properties relationships are the theme of solid state chemistry. Materials scientists and chemists have utilized an abundance of simple crystal structures to enhance understanding of chemical and structural origins of properties in materials for decades....
Lithium serves an unparalleled role for high energy-density storage applications and is vital for the continued advancement of the world economy. However, global supply is heavily reliant on lithium deposits situated in select locations, creating unpredictability in the price and concerns for the sustained production of the resource. Additionally, future...
Moral distress is the experience of knowing the right action to take but being unable to take it. It is especially prevalent in the healthcare profession, where professionals’ actions are limited by the wishes of patients and their families, hierarchies, and organizational failings. Since it is accepted that healthcare professionals...
Solid state inorganic oxides play an important role in next generation electronics based on their stability, versatility, and enhanced properties over other materials. However, in order to design or tune these materials for a desired functionality it is necessary to fully understand the structure behind the properties exhibited. This dissertation...
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...
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)...
Polyoxoniobates (PONbs) are attracting great attention in recent years due to its novelty as well as a variety of geometrical presentations in different pH conditions. In this paper we are reporting the reaction of tetramethyl-decaniobate ([(CH3)4N]6[Nb10O28]) with alkaline carbonates to observe the periodic trend of alkaline ions interacting with the...
Organotin clusters have attracted notable attention for use as inorganic photoresists. This dissertation discerns dimeric and dodecameric organotin clusters, [(n-C₄H₉Sn)(OH)(H₂O)Cl₂]₂ (Sn₂) and [(n-C₄H₉Sn)₁₂O₁₄ (OH)₆ ]+ (Sn₁₂), both of which are stable hydrolysis and condensation products of n-C₄H₉SnCl₃. This work identifies Sn₂ as a superior precursor choice for solution deposition of...
Atmospheric fine particulate matter (PM2.5) has been linked to the death of 7 million people per year around the planet. The organic portion of PM2.5 is responsible for increases in oxidative stress, inflammation, mutation and carcinogenesis. Anthropogenic activity releases more organic material into the atmosphere, and has increased the amount...
Metal-oxo clusters can be described as soluble pieces of metal-oxide frameworks. Currently, metal-oxo clusters are being considered as solution-based precursors for extreme ultraviolet (EUV, 13.5 nm) photoresist materials, which are a crucial component in the fabrication of microelectronic devices. Two different photoresist precursor systems have been investigated – alkyltin clusters...
With the rise of resistant bacterial pathogens, currently prescribed antibiotics are rendered useless. In recent years, marine natural products (MNPs) have emerged as novel sources for drug leads. The ocean is a complex environment where marine animals cohabitate with many, and sometimes harmful microorganisms and viruses, but resist infections. Developed...
Metal-oxo clusters are discrete molecular metal-oxides. Most metals form numerous cluster compounds that can be ligated, unligated, charged or neutral, controlling their solubility in water and/or organic solvents. They are important species to study reaction pathways from the monomeric building units to the bulk metal oxides, and have many application...
Dental plaque is one of the well-characterized biofilms in the human body. Oral bacterial species play vital roles in maintaining healthy bacterial homeostasis as well as causing oral infections. Many of the oral diseases are caused by opportunistic pathogens, and therefore, the bacterial metabolic activities become important in dictating their...
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...
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...
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...
Traffic exhaust is an important source of air pollution. This exposure assessment study examined traffic related air pollution in Curitiba, Brazil, and is particularly relevant due to 75% of the population using diesel public transportation. Traffic density was tabulated, and vehicle-type was distinguished based on their fuel type (diesel or...
Tethering fluorophores on metal nanoparticles for metal enhanced fluorescence (MEF) has attracted a lot of attention from scientists interested in fluorescence based approaches. MEF has many benefits in fluorescence related techniques, because the analytical signal increases and enables potentially lower detection limits or better sensitivity. Many types of nanoparticles have...
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...
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...
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...
Dearomatization reactions exist broadly in biosynthesis and chemical synthesis. The highly functionalized atoms of arenes can be masked by it aromaticity, and upon dearomatization, those reactive atoms can be readily applied to bond formation and further manipulation. The total synthesis of (–)-cephalotaxine and (–)- homoharringtonine is described via an oxidative...
In this dissertation, I describe the experimental investigation of large superfluid helium droplets. The goal and direction of this thesis is to facilitate the use of these droplets as part of our project ss-EDI. The overall scheme of ss-EDI is to dope proteins inside helium droplets and collect a diffraction...
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...
Aqueous film forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per-and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though they are more abundant (5-10% w/w) than PFASs (0.9-1.5% w /w) in...
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...
Part I of this dissertation includes the chronological synthetic background of mandelalide A as well as the synthesis of the C1-C14 glycosylated southern subunit of mandelalide. A key aspect of the synthesis includes a novel silver-catalyzed cyclization (AgCC) of a propargylic benzoate to construct the substituted cis-pyran ring system present...
Exploring bioactive natural products has contributed largely to clinically approved drugs we have been using over the last 100 years. Especially among the anti-infective drugs, around 70% of currently used antibiotics were discovered or derived from microbial secondary metabolites, among them compounds like vancomycin, chloramphenicol, and erythromycin. Facing the unavoidable...
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...
This work investigates the effect of cation substitution on the properties of the lead-free, solid solution (Na₀.₅Bi₀.₅)TiO₃-BaTiO₃ (NBT-BT). Substitution into NBT-BT increases disorder and increases the relaxor ferroelectric properties. These relaxor ferroelectric materials show large piezoelectric strains that can be utilized in actuator applications. Ceramic samples were prepared using standard...
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...