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Surface Engineering of Materials for Beyond-Microelectronics

Description: All oxide heterostructure Cr2O3/TiO2-x was deposited on Al2O3(0001) single crystal via MBE. The analysis of interfacial interactions involving two metal oxides resulting in magnetic properties gave insights for using such heterostructures as potential spintronic device materials. The corundum phase epitaxial growth of TiO2-x on Al2O3 was characterized using XPS, AES, EELS, and LEED. The data obtained gives evidence of presence of two-dimensional electron gas at titania surface due to oxygen vac… more
This item is restricted from view until January 1, 2029.
Date: December 2023
Creator: Anwar, Fatima

Synthesis, Characterization, Standardization, and Validation of Luminescence Optical Chemosensors for the Detection of Carbon Dioxide, Aluminum Ions, and Silver Ions for Real-Life Applications

Description: The presented dissertation encompasses three distinct investigations into novel complexes with diverse applications. Firstly, a Europium-based complex, K[Eu(hfa)4], exhibits remarkable potential for detecting dissolved CO2 in an ethylene glycol medium, offering a low limit of detection, rapid response times, and high signal-to-noise ratios. This complex demonstrates promise for quantifying CO2 concentrations and finds utility in sugar fermentation monitoring. Secondly, an innovative ratiometric… more
This item is restricted from view until January 1, 2025.
Date: December 2023
Creator: Perera, Nawagamu Appuhamilage Kasun

A Computational Study of Palladium (II) bis(NHC) Complexes and a Computational/Experimental Study of Gold (I) bisADC Complexes Utilizing Non-Covalent Interaction for Catalysis

Description: Carbene ligands over these years have become a heavily utilizes and effective ligand for catalysis. The diamino carbene class of ligands are slightly less understood. The effects of bis(carbene) ligand structures of palladium (II) catalysts were investigated using the ETS-NOCV method. The results showed that the amount of π-backbonding played a major role in the rate of the reaction for these NHC complexes. The amount of pi acceptance from the ligand increased in correlation to the length of th… more
This item is restricted from view until August 1, 2025.
Date: July 2023
Creator: Tiemann, Matthew Austin

Design and Synthesis of Gold (I) Acyclic Diamino Carbene Complexes as Metallodrugs for Cancer and for Asymmetric Catalysis

Description: Many previous studies have demonstrated that gold compounds possess successful results in catalysis and in medicinal chemistry. The central aim of this dissertation is the design and synthesis of novel gold (I) acyclic diamino carbene complexes as a chemotherapeutic agent for triple-negative breast cancer (TNBC) and for catalysis. In this study, a series of chiral neutral and cationic gold (I) acyclic diamino carbene (ADC) complexes and neutral gold (I) bis- ADC complexes have been synthesize… more
This item is restricted from view until August 1, 2025.
Date: July 2023
Creator: Asuramana Pedi Durayalage, Roshani
open access

β, β'-π-Extended Porphyrins: Exploration of Functionalization and Aromatic Character

Description: Seventeen new dithiophenyl- and napthodithiophenyl- fused porphyrins were synthesized; from these an additional 7 porphyrin oligomers were also synthesized. Additionally freebase 2,7-dimethoxytriphenylene fused porphyrin was also synthesized from a freebase precursor. Aromatic indices NICS and AICD were used to evaluate these new molecules.
Date: July 2023
Creator: Cooper, Courtney Taylor

Spectral, Electrochemical, and Photochemical Characterization of Donor-Acceptor Supramolecular Systems

Description: This dissertation research work focuses on the investigation of novel donor-acceptor systems elucidating their photochemical properties, anion binding, and their potential application in the development of artificial photosynthetic systems. The explored systems are based on oxoporphyrinogen (OxPs), porphyrins, fullerene, and boron dipyrromethene (BODIPY) based donor-acceptor systems. The photochemical properties of novel molecular systems were elucidated using UV-vis spectroscopy, fluorescence … more
This item is restricted from view until August 1, 2024.
Date: July 2023
Creator: Liyanage, Anuradha Vidyani

Synthesis and Studies of Platinum- and Palladium-Based Porphyrin-Fullerene Conjugates to Study the Long-Lived Charge-Separated States

Description: The research presented in the dissertation deals with the synthesis, characterization, photophysical, electrochemical, and pump probe studies of porphyrin-fullerene based donor-acceptor conjugates. The first chapter provides insights into the introduction of the thesis, which explains the events that occur in natural photosynthesis and the mimicking process of an artificial photosynthesis based on natural photosynthesis, works done in covalently and non-covalently linked donor acceptor systems,… more
Date: July 2023
Creator: Subedi, Dili Raj
open access

Synthesis, Kinetic Studies, and Structural Investigations of Osmium and Ruthenium Clusters

Description: Addition reactions of ten neutral nucleophiles and seven anionic nucleophiles with the pentaosmium pentadecacarbonyl carbido cluster Os5C(CO)15 have been kinetically studied and several important reactivity trends have been established. The calculated activation parameters support an associative mechanism involving the attack of nucleophiles on the parent cluster in the rate-limiting step. Decarbonylation reactions of neutral arachno clusters Os5C(CO)15L have also been kinetically studied and d… more
Date: July 2023
Creator: Nesterov, Volodymyr

Cleaner Futures: Covalent Organic Frameworks for Sustainable Degradation of Lignocellulosic Materials

Description: As countries pledge their commitment to a net-zero future, much of the previously forgotten climate change research were revitalized by efforts from both governmental and private sectors. In particular, the utilization of lignocellulosic materials saw a special spotlight in research interest for its abundance and its carbon removal capability during photosynthesis. The initial effort in mimicking enzymatic active sites of β-glucosidase will be explored. The crystalline covalent organic framewor… more
This item is restricted from view until June 1, 2028.
Date: May 2023
Creator: Lan, Pui Ching
open access

Magnetron Sputtering of Transition Metal Oxynitrides and Their Characterization with Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy

Description: Transition metal oxynitrides are of growing interest for their use as electrocatalyst for nitrogen reduction reaction. The metals in the oxynitride used for catalytic process are stabilized in intermediate state for effective activation of nitrogen. Therefore, studying the interaction of metal oxynitrides films to ambient exposure is necessary. Here, sputter deposited vanadium oxynitride is compared to cobalt oxynitride using insitu Auger electron spectroscopy (AES), ex situ X-ray photoelectron… more
Date: May 2023
Creator: Adesope, Qasim Adewale
open access

One-Step Synthesis of 1,3,4-Oxadiazines, 4,5,6,7-Tetrahydro-1h-Indoles, and Functionalized Benzo[B]Carbazoles Catalyzed by Rare Earth Metal Triflates and Cooperative Enamine-Bronsted Acid

Description: Design and development of novel one-step reactions that produce nitrogen-containing scaffolds is an invaluable area of chemistry due to the abundance of these moieties in natural products and biologically active molecules. Discovering novel methods using uncommon substrates and rare earth metals to access these significant scaffolds present a challenge. Over the course of my doctoral studies, I have designed, developed and optimized novel reactions by using rarely known substrates and rare eart… more
Date: May 2023
Creator: Cortes Vazquez, Jose

Porous Organic Polymer-based Nanotraps for Metal Resource Recovery/Extraction from Water

Description: The recovery processes of critical metals from multiple sources have turned more and more attention due to the increasing demand and consumption of them in modern industry. Many metals are used as significant components in manufacturing of a variety of products and equipment, playing significant roles in the economic security and national security; those metals involve rare earth elements (REEs), precious metals which include gold, silver, and platinum group metals (PGMs), and other valuable me… more
This item is restricted from view until June 1, 2025.
Date: May 2023
Creator: Song, Yanpei

Theoretical Studies of Photoactive Metal Complexes with Applications in C-H Functionalization and Quantum Computing

Description: Previous work was successful at delineating reaction pathways for the photoactivated synthesis of an amine, [CztBu(PyriPr)(NH2−PyriPr)], by double intramolecular C−H activation and functionalization via irradiating a metal(II) azido complex, [CztBu(PyriPr)2NiN3. The present work seeks to expand upon earlier research, and to substitute the metal with iron or cobalt, and to expand the study to photocatalyzed intermolecular C−H activation and functionalization of organic substrates. Density functi… more
This item is restricted from view until June 1, 2024.
Date: May 2023
Creator: Alamo Velazquez, Domllermut C.

Aromaticity, Supramolecular Stacks, and Luminescence Properties of Cyclic Trinuclear Complexes

Description: The dissertation covers three major topics: metal-assisted aromaticity, synthetic approaches to tailor donor-acceptor supramolecular stacks, and photoluminescence properties of cyclic trinuclear complexes (CTCs) of d10 metals. First, multiple theoretical approaches are adapted to discuss in detail the origin of aromaticity of CTCs, putting forward a metal-assisted aromaticity model. Next are the discoveries of donor-acceptor stacked CTC–CTC' complexes from both experimental and computational pe… more
Date: December 2022
Creator: Lu, Zhou

An Investigation into the Micromechanical and Corrosion Properties of Additively Manufactured Stainless Steel 316L

Description: In this thesis, micro-mechanical properties and corrosion resistance of laser powder bed fusion (L-PBF) processed additive manufactured (AM) 316L stainless steel parts were investigated for different combinations of processing parameters. Various laser powers were employed for the fabrication of all AM 316L stainless steel parts. Nanoindentation, areal roughness, and electron backscattered diffraction (EBSD) characterization were used to characterize the surface of the AM samples prior to corro… more
This item is restricted from view until January 1, 2028.
Date: December 2022
Creator: England, Jennifer

Investigation of Ionic Liquid Phases for Chromatographic Separation of Fentanyl Analogues

Description: Opioid abuse and in particular fentanyl, a synthetic opioid, has been of concern in the last decade. Fentanyl is an illicit drug of concern to due to its prevalence and potency. Research to date has focused on supporting law enforcement by developing methods suitable for chemical profiling and identifying fentanyl from various matrices. However, methods geared towards analysis of fentanyl isomeric analogues are rare. Analysis of isomers is challenging due to similar mass spectral fragmentation … more
This item is restricted from view until January 1, 2028.
Date: December 2022
Creator: Smart, Katherine Rose

Nanofluidic Membrane Based on Covalent Organic Framework: Design Strategies and Applications

Description: Nanofluidic is an emerging field of applying fluid properties in nanochannels or nanostructures. The nanoporous channel with a pore size of less than 100 nm will strongly affect the motion of the fluid. Meanwhile, the pore environment, such as hydrophilic and hydrophobic properties, charge density, and host-guest recognition would be crucial for the transportation of molecules and ions in the pore. This thesis is focused on the synthesis, characterization of nanofluidic membranes and their appl… more
Date: December 2022
Creator: Zhu, Changjia

Parameterization of Ionic Liquids and Applications in Various Chemical Systems

Description: In this work, the development of parameters for a series of imidazolium-based ionic liquids molecules, now included in the AMOEBA force field, is discussed. The quality of obtained parameters is tested in a variety of calculations to reproduce structural, thermodynamic, and transport properties. First, it is proposed a novel method to parameterize in a faster, and more efficient way parameters for the AMOEBA force field that can be applied to any imidazolim-based cation. Second, AMOEBA-IL polar… more
This item is restricted from view until January 1, 2028.
Date: December 2022
Creator: Vazquez Cervantes, Jose Enrique

Porous Materials as Drug Delivery Systems

Description: The porous materials discussed in this dissertation are metal-organic frameworks (MOFs) and porous liquids. Due to their high surface areas, tunable structures, and controllable porosities, MOFs have been explored for a wide variety of drug delivery applications. In chapter 2, MOFs have been used as magnetothermal-triggered release carriers through spatially distributed iron oxide nanoparticles within MOF matrix as a magnetic heating mediator and surface-grafted thermal-responsive nanocap as an… more
This item is restricted from view until January 1, 2028.
Date: December 2022
Creator: Ge, Xueying
open access

Ranaspumin Protein Characterization and Applications for Both Environmental and Medical Purposes

Description: The Túngara frog (Engystomops pustulosus) from Central America creates a bio-foam that protects their young from dehydration, microbial degradation, and even predators during early development. The foam is composed of unique proteins known as Ranaspumin 1-6 (RSN 1-6). These RSN proteins have been synthetically synthesized and verified with Circular Dichroism (CD) to determine their critical micelle concentration, antimicrobial properties, and stability at varying temperatures and pH ranges. Thr… more
Date: December 2022
Creator: Koerber, Rachel

Sulfur-Based Organic Compounds as Novel Corrosion Inhibitors for Brass and Aluminum Alloy Protection in Acid Cleaning Solutions

Description: In this study, thiol and two disulfide compounds have been tested as new corrosion inhibitors for brass and aluminum alloys. Pyridine-2-thiol and 2,2'-dipyridyl disulfide were tested for brass alloys in 0.5 M H2SO4 solution and both inhibitors showed excellent corrosion protection against the aggressive corrosive ion attack. Both inhibitors adsorbed to brass surface forming a protective film via a chemisorption process. XPS studies showed formation of Cu-S bond which allows these molecules to c… more
This item is restricted from view until January 1, 2028.
Date: December 2022
Creator: Karunarathne, Darshan Jayasinghe

Bifunctional Enamine‐Metal Lewis Acid Catalysis and α-Enaminones for Cyclization Reactions

Description: The use of enamines continues to be an important tool in organic syntheses as both a catalyst and reactant. The addition of metal catalysts coupled with enamine catalysis has generated many reactions that normally would not occur separately. However, catalysts' incompatibility is an issue that we wish to solve allowing new chemistry to occur without hindrance. The use of enamines has continued to be a well-studied area of organic chemistry, but the field is ripe for different types of enamines … more
This item is restricted from view until September 1, 2024.
Date: August 2022
Creator: Davis, Jacqkis

Chemically Optimized Cu Etch Bath Systems for High-Density Interconnects and the FTIR Operando Exploration of the Nitrogen Reduction Reaction on a Vanadium Oxynitride Electrocatalyst

Description: Printed circuit board manufacturing involves subtractive copper (Cu) etching where fine features are developed with a specific spatial resolution and etch profile of the Cu interconnects. A UV-Vis ATR metrology, to characterize the chemical transitions, has been developed to monitor the state of the bath by an in-situ measurement. This method provides a direct correlation of the Cu etch bath and was able to predict a 35% lower etch rate that was not predicted by the three current monitoring met… more
This item is restricted from view until September 1, 2027.
Date: August 2022
Creator: Caperton, Joshua M

Computational Investigations of Catalytic Activity by Metal-Containing Complexes

Description: This dissertation delves into the catalytic activity of multiple metal-containing complexes with an emphasis on the activation of C–H bonds in small molecules and olefin oligomerization. The research contained in these works employs computational methodologies to better understand the thermodynamics and kinetics of the reactions. Computations can be used to quickly identify novel models and find ideal substitutions for improved catalyst design. Within this dissertation, multiple molecules of di… more
Date: August 2022
Creator: Carter, Carly Catherine
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