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...
The total kinetic energy release and fission mass distributions for the fast neutron (En = 3–100 MeV) induced fission of 232Th, 233U, 235U, 237Np, 239Pu, 240Pu, and 242Pu have been measured using the LANSCE facility. The neutron energies were deduced from time-of- flight measurements. The fission fragments were detected using...
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....
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...
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 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...
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...
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-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...
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...
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...
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 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...
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,...
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...
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...
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,...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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...
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...
Linden (Tilia spp.), a profusely flowering temperate tree that provides bees with vital pollen and nectar, has been associated with bumble bee (Bombus spp.) mortality in Europe and North America. Bee deaths have been attributed, with inadequate evidence, to toxicity from mannose in nectar or starvation due to low nectar...
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)...
Faculty research has led to a plethora of innovations and entrepreneurial resources (I&E), allowing for enhancements to the greater social good including, but not limited to, technological and economic advancements. Faculty I&E also enhances faculty competitiveness for funding, institutional image and fundraising, and supports students’ workforce preparation. Over time institutions...
Researcher innovation and leadership skills are fundamental to create implementable solutions to pressing societal- and market-based global problems. The Research to Innovation to Society
(R2I2S) program is a transformative approach to graduate education, training students at the intersection of research, innovation, and leadership. We detail the design of the program,...
We call for the promotion of faculty innovation & entrepreneurship (I&E), across disciplines, and its recognition in promotion and tenure processes– thereby enabling universities to better serve as a talent and idea engine for the Nation’s innovation economy, and evolve and respond in a time of enhanced societal needs and...
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...