Physical Sciences and Mathematics Commons^™

Photoluminescent Zirconium Complexes For Visible Light Photoredox Catalysis, Yu Zhang

Graduate Theses, Dissertations, and Problem Reports

Early transition metals like zirconium are attractive candidates for the design of luminescent molecules based on earth-abundant elements. Here, a series of zirconium complexes carrying two pyrrolyl-based ligands have been synthesized and characterized. These complexes are photoluminescent upon excitation with visible light and exhibit remarkably long emission lifetimes of hundreds of μs in solution at room temperature. Computational studies using time-dependent density functional theory (TD-DFT) were conducted to identify the nature of the luminescent excited states as mixed intra-ligand/ligand-to-metal charge-transfer (ILCT/LMCT) states. The electrochemistry studies revealed multiple reversible redox events for each zirconium complex. Furthermore, the excited state of the …

Compound-Specific Isotope Analysis Of Amino Acids In Biological Tissues: Applications In Forensic Entomology, Food Authentication And Soft-Biometrics In Humans, Mayara Patricia Viana De Matos

Graduate Theses, Dissertations, and Problem Reports

In this work we demonstrate the power of compound-specific isotope analysis (CSIA) to analyze proteinaceous biological materials in three distinct forensic applications, including: 1) linking necrophagous blow flies in different life stages to their primary carrion diet; 2) identifying the harvesting area of oysters for food authentication purposes; and 3) the ability to predict biometric traits about humans from their hair.

In the first application, we measured the amino-acid-level fractionation that occurs at each major life stage of Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) blow flies. Adult blow flies oviposited on raw pork muscle, beef muscle, or chicken liver. Larvae, pupae …

Electrochemical Detection Of Fentanyl Using Screen-Printed Carbon Electrodes With Confirmatory Analysis Of Fentanyl And Its Analogs In Oral Fluid Using Liquid Chromatography-Tandem Mass Spectrometry, Colby E. Ott

Graduate Theses, Dissertations, and Problem Reports

Utilizing screen-printed carbon electrodes (SPCEs), a fast, simple, and sensitive approach toward the detection, identification, and quasi-quantitation of fentanyl was achieved both in an electrochemical cell and as a drop on the electrode surface. Electro-oxidation of fentanyl at the electrode was demonstrated using adsorptive stripping square-wave voltammetry between -0.5 V and +1.6 V with 100 mM Tris-HCl buffer at pH 8.5 as supporting electrolyte. Parameter optimization was conducted during method development to include supporting electrolyte and pH, electrochemical technique, pre-treatment and equilibration time, and various surface modifications. The simplest method utilizing an unmodified SPCE was determined to be appropriate for …

Non-Target Analyses Of Novel Psychoactive Substances; Inherent Variation In Gcms Relative Abundances And Gas Phase Hydrogen Deuterium Exchange Isomer Discrimination, Kristin Michelle Kelly

Graduate Theses, Dissertations, and Problem Reports

Novel psychoactive substances (NPSs) are synthetically derived compounds designed to mimic the effects of other illicit drugs. An endless cycle of NPSs continually reach the drug market due to limitations in drug legislation creating two problems: (1) non-availability of standards and (2) multiple isobars indistinguishable even to high resolution mass spectrometry. Gas chromatography-mass spectrometry (GCMS) is the most common instrument used for compound identification in non-targeted seized drug analysis. Compound identification using this technique relies on mass spectra where the percent relative abundances (%RAs) of all m/z values are compared manually or searched against a library database. Lacking standards, laboratories …

Identification Of Burnt Smokeless Gunpowders Through Physical Characteristics, Cameron Taylor Hartwig

Graduate Theses, Dissertations, and Problem Reports

Firearms are one of the most commonly used weapons by violent criminals throughout the United States. In crimes involving the discharge of a firearm, residues from the combustion products are deposited on the shooter and in the firing direction. Some of the residues left behind are unburnt and partially burnt particles of the propellant. The most common propellant used in modern firearms is smokeless powder. The identification of particles as smokeless powder and the determination of the brand of the powder are two ways a forensic examiner may be able to utilize smokeless powder evidence. The determination of the brand …

Construction Of Trisubstituted Chromone Skeletons Carrying Electron-Withdrawing Groups Via Phio-Mediated Dehydrogenation And Its Application To The Synthesis Of Frutinone A, Qiao Li, Chen Zhuang, Donghua Wang, Wei Zhang, Rongxuan Jia, Fengxia Sun, Yilin Zhang, Yunfei Du

Faculty & Staff Scholarship

Abstract

The construction of the biologically interesting chromone skeleton was realized by PhIO-mediated dehydrogenation of chromanones under mild conditions. Interestingly, this method also found application in the synthesis of the naturally occurring frutinone A.

Effect Of Bulk Composition On The Heterogeneous Oxidation Of Semi-Solid Atmospheric Aerosols, Hanyu Fan, Fabien Goulay

Faculty & Staff Scholarship

Abstract: The OH-initiated heterogeneous oxidation of semi-solid saccharide particles with varying bulk compositions was investigated in an atmospheric pressure flow tube at 30% relative humidity. Reactive uptake coefficients were determined from the rate loss of the saccharide reactants measured by mass spectrometry at different monosaccharide (methyl-β-d-glucopyranoside, C7H14O6) and disaccharide (lactose, C12H22O11) molar ratios. The reactive uptake for the monosaccharide was found to decrease from 0.53 ± 0.10 to 0.05 ± 0.06 as the mono-to-disaccharide molar ratio changed from 8:1 to 1:1. A reaction–diffusion model was developed in order to determine the effect of chemical composition on the reactive uptake. The …

Experimental And Modeling Investigation Of The Oh-Initiated Oxidation Of Semi-Solid And Aqueous Saccharide Aerosols, Hanyu Fan

Graduate Theses, Dissertations, and Problem Reports

My research focuses on investigating the impact of moisture-induced and oligomer-induced viscosity changes on OH-initiated oxidation of semi-solid aerosols,and the role of gas-liquid interfaces in regulating aqueous aerosol chemistry. Saccharides, which are a major constituent of aqueous atmospheric aerosols, are chosen as model molecules to form highly oxygenated organic aerosols. The experiments are performed using an atmospheric pressure flow-tube reactor with both online VUV-AMS (Vacuum-Ultraviolet Aerosol Mass Spectrometer) and offline GC-MS analysis techniques. The decay rates of saccharide are determined by measuring the loss signal of saccharide in the particle phase as a function of OH exposure (time-integrated total concentration …

Copper-Catalyzed Regioselective Boracarboxylation Of Vinyl Arenes: Catalytic Efficiency And Synthetic Utility, Trina M. Perrone

Graduate Theses, Dissertations, and Problem Reports

Hetero(element) carboxylation is an appealing transformation that involves the installation of CO2 and another hetero(element) in one step. This transition metal-catalyzed one-pot synthesis provides a route to achieve highly functionalized carboxylic acid products with an abundant and cheap C1 feedstock. This difunctionalization also avoids the use of reactive metal hydride species, which is a prominent limitation of hydrocarboxylation chemistry. A copper-catalyzed regioselective boracarboxylation of vinyl arenes has been developed to access pharmaceutically relevant β-boryl-α-aryl propionic acid products. One drawback of this reaction is the necessity for high catalyst loading to achieve catalytic turnover. To circumvent this issue, the reduction of …

In Situ Infrared Spectroscopic Study Of Iron-Catalyzed Hydromagnesiation Of Vinyl Arenes, Jessica Ann Rogers

Graduate Theses, Dissertations, and Problem Reports

Iron catalysis, especially homogeneous catalysis, has been a resurging topic of organometallic chemistry research. Discussions of past and present mechanistic analyses for homogeneous iron catalysis will be discussed in Chapter 1. As an expansion of homogeneous iron catalysis, in situ infrared spectroscopy will be used to develop a full mechanistic study of iron-catalyzed hydromagnesiation of vinyl arenes. The kinetic analyses by both initial and observed rate measurements indicate complex concentration dependencies on the (PDI)iron catalyst as well as sacrificial Grignard reagent and styrene. These complexities are not limited to non-linear catalyst and Grignard initial rate and inhibition by styrene/Grignard at …

The Impact Of Post Translational Modification On The Aggregation Of The Ss-Amyloid Peptide In The Presence Or Absence Of Lipids, Albert Walton Pilkington Iv

Graduate Theses, Dissertations, and Problem Reports

Alzheimer’s disease (AD) is a neurodegenerative condition afflicting 5.7 million Americans with no effective treatments. The pathology of AD is described by the formation of neurotoxic oligomers formed by the self-assembly of amyloid-β (Aβ). The affinity of oligomers for cellular membranes disrupts calcium homeostasis and is believed to be the underlying cause of neurotoxicity; however, due to the metastability of oligomers, it has been difficult to understand their role in membrane interactions and self-assembly. Here we utilize post translational modifications (PTM) to understand the role of specific amino acids on Aβ₄₀-membrane interactions and self-assembly. We employ ThT, AFM, …

Construction Of A Cross-Layer Linked G-Octamer Via Conformational Control: A Stable G-Quadruplex In H-Bond Competitive Solvents, Ying He, Yanbin Zhang, Luksaz Wojtas, Novruz G. Akhmedov, David Thai, Heng Wang, Xiaopeng Li, Hao Guo, Xiaodong Shi

Faculty & Staff Scholarship

Methanol soluble and stable guanosine octamers were successfully achieved via H-bond self-assembly. Through structural conformational design, we developed a new class of guanosine derivatives with modification on guanine (8-aryl) and ribose (20 ,30 -isopropylidene). This unique design led to the formation of the first discrete G8-octamer with its structure characterized by single crystal X-ray diffraction, MS and NMR spectroscopy. The G8-octamer showed unique cation recognition properties, including the formation of a stable Rb+ templated G-quadruplex. Based on this observation, further modification on the 8-aryl moiety was performed to incorporate a cross-layer H-bond or covalent linkage. Similar G-octamers were obtained in …