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Donor-Acceptor Artificial Photosynthetic Systems: Ultrafast Energy and Electron Transfer (open access)

Donor-Acceptor Artificial Photosynthetic Systems: Ultrafast Energy and Electron Transfer

Mother nature has laid out a beautiful blueprint to capture sunlight and convert to usable form of energy. Inspired by nature, donor-acceptor systems are predominantly studied for their light harvesting applications. This dissertation explores new donor-acceptor systems by studying their photochemical properties useful in building artificial photosynthetic systems. The systems studied are divided into phthalocyanine-porphyrin-fullerene-based, perylenediimide-based, and aluminum porphyrin-based donor-acceptor systems. Further effect of solvents in determining the energy or electron transfer was studied in chapter 6. Such complex photosynthetic analogues are designed and characterized using UV-vis, fluorescence spectroscopy, differential pulse voltammetry and cyclic voltammetry. Using ultrafast transient absorption spectroscopy, the excited state properties are explored. The information obtained from the current study is critical in getting one step closer to building affordable and sustainable solar energy harvesting devices which could easily unravel the current energy demands.
Date: December 2021
Creator: Seetharaman, Sairaman
System: The UNT Digital Library
Predictive Modeling of Novel Mutations to DNA-Editing Metalloenzymes and Development of Improved QM/MM Methods (open access)

Predictive Modeling of Novel Mutations to DNA-Editing Metalloenzymes and Development of Improved QM/MM Methods

Molecular dynamics simulations and QM/MM calculations can provide insights into the structure and function of enzymes as well as changes due to mutations of the protein sequence.
Date: December 2021
Creator: Hix, Mark Alan
System: The UNT Digital Library
Linearly-Annulated, Functionalized, β,β'-π-Extended Porphyrins (open access)

Linearly-Annulated, Functionalized, β,β'-π-Extended Porphyrins

Benzannulation to porphyrin 2,3 positions has previously been accomplished using various methodologies in the past century, yet there remain limited methodologies to both annulate to the porphyrin periphery and add functional moieties that can then be derivatized for diverse applications. This dissertation describes the development of synthetic routes and characterization of a variety of linearly-annulated, functionalized, β,β'-π-extended porphyrins. There are five chapters in this dissertation, the first of which introduces synthesis and properties of porphyrins and π-extended porphyrins. Chapter 2 describes synthesis of pentacenequinone-fused and pentacene-fused poprhyrins with distinct and new optical absorbance properties. In chapter 3, synthesis and characterization of benzimidazole-fused porphyrins displaying external metal binding capability is described. The synthetic method developed in chapter 3 is extended in chapter 4 to synthesis of bisbenzimidazole-fused porphyrin dimers that show split Soret character, likely due to excitonic coupling between porphyrins of the dimer. Chapter 5 summarizes this dissertation and describes future directions that this dissertation provides foundation for.
Date: December 2021
Creator: Moss, Austen Edmond
System: The UNT Digital Library
Computational Studies of the Photophysical, Structural, and Catalytic Properties of Complex Chemical Systems (open access)

Computational Studies of the Photophysical, Structural, and Catalytic Properties of Complex Chemical Systems

Computational chemistry employs mathematical algorithms, statistics, and large databases to integrate chemical theory with experimental observations. Computational modeling allows us to make predictions concerning molecular properties and reactivity that ultimately lead to accurate assessment of the most important fundamental properties of chemical systems. Advances in theoretical techniques and computer power have dramatically increased the usefulness and importance of computational chemistry as a complement to experimental studies. This is especially relevant to catalytic reactions of industrial importance as well as the analysis of structural properties and the resulting spectroscopic phenomena in what are often otherwise counterintuitive models. This dissertation is a representation of the research I performed during my years as a graduate student in the Chemistry Department at the University of North Texas. My research has examined novel carbenes as efficient organocatalysts, structure-based design and optimization of small molecule drugs, and surveying methods to accurately describe structure and bonding and catalytic abilities of inorganic and organometallic systems. The works presented herein have been published or are awaiting submission to peer-reviewed scientific journals. A variety of computational techniques were employed in studying metal-mediated catalysis and organocatalysis as well as the structural and photophysical properties of systems containing closed-shell transition metal ions.
Date: May 2021
Creator: Melancon, Kortney
System: The UNT Digital Library
Instrumental Development and Implementation of Portable Membrane Inlet Mass Spectrometry for Homeland Security and Environmental Applications (open access)

Instrumental Development and Implementation of Portable Membrane Inlet Mass Spectrometry for Homeland Security and Environmental Applications

A rapidly growing topic of great interest is the adaptation of benchtop analytical instrumentation for use in outdoor harsh environments. Some of the areas that stand to benefit from field instrumentation development include government agencies involved with the preservation of the environment and institutions responsible for the safety of the general public. Detection systems are at the forefront of the miniaturization movement as the interest in analyte identification and quantitation appears to only be accessible through the use of analytical instrumentation. Mass spectrometry is a distinguished analytical technique known for its ability to detect the mass-to-charge (m/z) ratios of gas-phase ions of interest. Although these systems have been routinely limited to research lab-based analysis, there has been considerable development of miniaturized and portable mass spectrometry systems. Membrane Inlet Mass Spectrometry (MIMS) is becoming a common method of sample introduction that is subject to significant development. MIMS allows for minimal sample preparation, continuous sampling, and excludes complicated analyte introduction techniques. Sampling is accomplished using a semipermeable membrane that allows selective analyte passage into the vacuum of the mass spectrometer. MIMS is becoming the preeminent choice of homeland security and environmental monitoring applications with increasing opportunities for the future development of specialized …
Date: December 2021
Creator: Anguiano Virgen, Camila
System: The UNT Digital Library

Corrosion Mechanism and Prevention of Wire Bonded Device in Microelectronic Manufacturing and Spectroscopic Investigation of Copper Etch Chemical Equilibria for High Density Interconnect Application

In the first part of this dissertation work, Al bond pad corrosion behavior was investigated in the presence of common industrial contaminants such as chloride (Cl-) and fluoride (F-). Al corrosion while in direct contact with Cu displayed rapid hydrogen (H2) gas evolution and dendrite propagation. In contrast, Al without bimetallic contact showed only minor surface roughening. This observed difference in the corrosion mechanism between Cl- and F- is attributed to the solubility of the corrosion products (AlCl3 vs. AlF3) formed on the Al surface. Our subsequent work explored corrosion prevention inhibition of wire-bonded devices (WBD) in the Cl- environment. Our research shows that the Al bond pad was protected against corrosion by chemically modifying the surface of the Cu wires, thereby preventing the H2 evolution. The inhibitor was observed to be highly selective, thermally stable, hydrophobic, and cost-effective, making it viable for industrial application of this coating for Al bond pad corrosion prevention. In the second part of the dissertation work, we utilized a novel approach of using ultraviolet-visible spectroscopy (UV-Vis) as a chemical-sensitive monitoring tool of the chemical environment in Cu etch bath. The UV-Vis technique illuminates the roles of H+, Cl-, Cu+, and Cu2+ to the etch …
Date: December 2021
Creator: Ashok Kumar, Goutham Issac
System: The UNT Digital Library
The Abraham Solvation Model Used for Prediction of Solvent-Solute Interactions and New Methods for Updating Parameters (open access)

The Abraham Solvation Model Used for Prediction of Solvent-Solute Interactions and New Methods for Updating Parameters

The Abraham solvation model (ABSM) is an experimentally derived predictive model used to help predict various solute properties. This work covers various uses for the ABSM including predicting molar enthalpies of vaporization, predicting solvent coefficients for two new solvents (2,2,5,5-tetramethyloxolane and diethyl carbonate), predicting values for multiple new ionic liquids (ILs). This work also introduces a novel method for updating IL ABSM parameters by updating cation- and anion-specific values using linear algebra and binary matrices.
Date: May 2021
Creator: Churchill, Brittani N.
System: The UNT Digital Library
Theoretical Thermochemistry of Tungsten Including σ and π Bond Components (open access)

Theoretical Thermochemistry of Tungsten Including σ and π Bond Components

Computational chemistry examination of the bond dissociation enthalpies of tungsten and main group elements. Includes quantification and calibration of theoretical methods to address the question of bond strengths including component σ and π molecular bonds.
Date: August 2021
Creator: Moulder, Catherine Anne
System: The UNT Digital Library

Pressure Controlled Topochemical Polymerization in Two-Dimensional Hybrid Perovskite

Mechanical pressure offers unique control over the energy landscape of chemical reactions, opening up pathways that are inaccessible through conventional thermochemistry. We hypothesize that the reduced dimensionality defines the conformational space of the high-pressure reaction, giving rise to new selectivity that is unavailable in 3D systems. Here, we demonstrate this concept through the pressure-controlled topochemical polymerization of the diacetylene molecule deca‐3,5‐diyn‐1‐amine (DDA) incorporated in the two-dimensional (2D) perovskite [DDA]2PbBr4. Compression at 3 GPa drives the first topochemical polymerization through 1,2 addition, forming a polyene product at room temperature. The reaction is initiated by the mechanical bending of the linear DDA molecule, a mechanism fundamentally different from the 1,4-addition in 3D solids. Importantly, pressure hinders the second 1,2-addition by disfavoring the gauche conformation between the remaining acetylene groups, allowing for the selective formation of polyene versus polyacene products. We characterize the reaction mechanisms and products using spectroscopies (Raman, X-ray photoelectron, ultraviolet-visible), X-ray diffraction and density-functional theory simulations. These results highlight the important role of dimensionality in high-pressure chemistry, and offers a new paradigm for creating low-dimensional functional materials.
Date: December 2021
Creator: Abu-Amara, Lama Marwan
System: The UNT Digital Library