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...
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...
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...
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...
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...
Nanostars have many potential applications, particularly in biomedicine, such as drug delivery, detection assays, and even cancer treatment. Seeing how their plasmon changes in response to changes to the environment of the nanostars can give us an insight to the stability of the nanostars. Our current studies involve the effect...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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)...
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...
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...
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...
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...
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...
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...
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....
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...
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...
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...
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...
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...
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...
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 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,...
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...
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...
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...
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...
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)...
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...
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...
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...
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...
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...