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...
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...
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...
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...
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 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...