Chemistry Commons^™

Design, Synthesis And Characterization Of Zinc And Gold-Based Metal Organic Frameworks And Complexes For The Detection And Treatment Of Cancer, May Reda Mohamed

Dissertations

The early detection of cancer plays a pivotal role in improving patient outcomes, emphasizing the urgent need for highly sensitive and selective biosensing platforms. Metal-Organic Frameworks (MOFs) have emerged as promising candidates in this domain due to their tunable properties, large surface area, and high porosity. Herein, the utilization of zinc-based MOF as a sophisticated biosensing platform tailored for the precise detection of the HER2 cancer biomarker is presented. HER2, a critical protein marker in breast cancer diagnostics and treatment, demands highly selective and accurate detection methods for effective patient management. Simple hydrothermal synthesis methodology has been adopted to synthetize …

Development Of Highly Efficient Hybridfunctionalized Membranes For Sustainable Water Harvesting, Ahmed Z. Abuibaid

Dissertations

Water scarcity has emerged as a critical global challenge. This problem catches the world's interest through events such as the severe drought in Europe during the summer of 2022. While desalination plants offer a solution, their high energy consumption necessitates the exploration of alternative, sustainable water resources. Addressing the urgent need for alternative water resources in the face of increasing water scarcity. A viable option was presented by fog harvesting, which is a method to collect water from atmospheric fog. This method was initially developed to meet the demands of a variety of sectors such as agricultural purposes, and household …

A Molecular Dynamics Study On The Destruction Mechanism Of Per And Polyfluoroalkyl Substances Due To Ultrasound Technology, Bruno Bezerra De Souza

Dissertations

Per- and polyfluoroalkyl substances (PFAS) are a group of stable synthetic chemicals that are highly persistent and harmful pollutants to the environment and human health. PFAS have caused a strong public and regulatory response due to their ubiquitous presence in the environment and toxicity to humans. The application of ultrasound is one of the most effective treatment technologies for the mineralization of PFAS in contaminated water. However, this technology is treated as a black box causing the inability to be optimized. Therefore, there is a pressing need to investigate the intricate dynamics of PFAS degradation under ultrasound to unlock its …

Molecular-To-Continuum Scale Modeling Of Aerosols: Atmospheric Application And Beyond, Ella Ivanova

Dissertations

Aerosol modeling is critical for various applications, such as climate forecasting, air quality, and human health impact assessment. During their lifetime, aerosols undergo a complex evolution, usually divided into several stages — formation, processing, transport, and removal — that occur on different scales. Thus, the choice of modeling methods depends on the stage considered. For example, certain stages of particle formation may require nano-scale modeling while aerosol-cloud interactions span from microscale to mesoscale. This study examines the modeling of aerosol behavior over a wide range of scales, from nano to microscale, with implications to mesoscale.

This dissertation focuses on two …

The Effects Of Free Volume And Processing On The Development Of Gas Separation Membranes, Jacob Schekman

Dissertations

Structure, thermal, mechanical, gas transport, and free volume properties of thiol-ene based systems are investigated and discussed. In the pursuit of generating low energy-cost polymer membranes for gas separation, it became apparent that UV-curing of thiol-ene materials presented several routes toward achieving this goal. Network structure plays a vital role in determining the gas transport properties of membrane materials. UV photopolymerization techniques provide a means to rapidly vitrify network morphologies which can be tuned depending on choice of monomer. Thiol-ene monomers offer a broad range of precursor materials from which to choose for the design of functional membrane materials.

Chapter …

Enabling High-Rate Thermoplastic Composite Manufacturing Through Structure-Processing-Property Relationships Of Polyphenylene Sulfide, Lina Ghanbari

Dissertations

In this dissertation, relationships between polyphenylene sulfide (PPS) chain structure and melt processing parameters are linked to thermoplastic composite (TPC) properties and mechanical performance. Deviations from linear PPS structure and the formation of branching/crosslinked moieties upon exposure to TPC manufacturing steps presents an opportunity to systematically uncover the interdependencies of melt-state thermal history on polymer rheology, crystallization, crystal structure, and translate these properties to the continuum level. This work first explores unreinforced PPS and how the formation of non-linear chain architectures yield altered rheological states when held at melt processing temperatures. These hindered chains exhibit unconventional crystallization behavior and non-uniform …

Design, Synthesis, And Optimization Of Allosteric Inhibitors Of Hiv-1 Integrase, Krunal H. Patel

Dissertations

The human immunodeficiency virus type 1 (HIV-1) infection remains a global health crisis, necessitating the development of innovative antiviral strategies. During the integration step, HIV-1 integrase (IN) interacts with viral DNA and the cellular cofactor LEDGF/p75 to effectively integrate the reverse transcript into the host chromatin. Recently, a novel class of antiretroviral agents called Allosteric Inhibitors of HIV-1 Integrase (ALLINI) compounds has emerged as a promising avenue in the fight against HIV-1. While originally designed to inhibit IN-LEDGF/p75 interactions, these compounds have been shown to also impact late-stage viral maturation severely through IN multimerization. Induction of IN multimerization interferes with …

Synthesis And Characterization Of Heavy-Metal Oxoanion- And Phosphonate-Binding Nanojars, Pooja Singh

Dissertations

Nanojars are an emerging class of anion-binding and extraction agents. These supramolecular coordination complexes (2 nm wide) exhibit exceptional anion binding strength that points to their possible application in the recovery of toxic or valuable anions from water bodies. Nanojars of the formula (TBA)2[XO3/42−⸦{CuII(μ-OH)(μ-pyrazolate)}n] (TBA = tetrabutylammonium cation; XO3/42− = anion; X = Se, Te, Cr, Mo, W, HP, HAs, HV; n = 26 – 36) are synthesized from Cu2+, OH−, pyrazole and the TBA salts of various anions. Nanojars possess hydrophobic exteriors with an array of pyrazolate ligands and hydrophilic interiors with a …

Development Of Novel Protein Digestion And Quantitation Methods For Mass Spectrometic Analysis, Yongling Ai

Dissertations

Proteins are the workhorses of biology, playing multifaceted roles in maintaining cellular function, signaling, and response to environmental cues. Understanding their abundance and dynamics is pivotal for unraveling the complexities of biological processes, which underpins the foundations of molecular and cellular biology. Accurate measurement of protein quantities provides insights into cellular homeostasis, facilitates the discovery of biomarkers, and sheds light on the molecular mechanisms of diseases, bridging the gap between the molecular intricacies of proteins and their functional consequences in health and disease. The evolution of protein quantitation methodologies, from classical colorimetric assays to sophisticated mass spectrometry-based approaches, has expanded …

New Methods For Stereoselective Glycosylation In Application To Significant Biomedical Targets, Melanie L. Shadrick

Dissertations

Glycosyl halides have been utilized for glycosylation reactions since the early studies by Arthur Michael, nearing the end of the 19^th century. Koenigs and Knorr then utilized silver salts to activate glycosyl bromides and chlorides to create synthetic glycosides. Many efforts to improve the outcome of reactions with glycosyl halides have emerged. The key emphasis has traditionally been placed on reaction rates, product yields, and stereocontrol. Recently, our lab reported that silver(I) oxide-mediated Koenigs-Knorr glycosylation reaction can be dramatically accelerated in the presence of catalytic acid additives. Methods to improve glycosylation was explored using mannosyl and glucosyl bromides. However, …

Binding Interactions Of Biologically Relevant Molecules Studied Using Surface-Modified And Nanostructured Surfaces, Palak Sondhi

Dissertations

This research focuses on the field of surface nanobioscience, wherein different nanosurfaces that will be used as working electrodes in the electrochemical cell are manufactured and surface modified to understand the critical binding interactions between biologically significant molecules like proteins, carbohydrates, small drug molecules, and glycoproteins. This research is essential if we are to determine whether a synthetic molecule can serve as a therapeutic candidate or diagnose a disease in its early stages. In order to fully understand the binding interactions, the study begins with defining some of the fundamental concepts, principles, and analytical tools for biosensing.

Afterwards, we addressed …

Interactions Of Lewis Acids And Carbonyls In The Presence Of Ligands Or Additives: How Solution Behavior Differs And The Implication On Catalytic Systems, Sophi Rose Todtz

Dissertations

Lewis acids have proven extremely valuable to the field of organic synthesis. Their diverse application in reactions of carbonyl-containing substrates has caused a multitude of efforts towards characterization of solution interactions between Lewis bases and Lewis acids. Though Lewis initially described a 1:1 interaction between one acid and one base, our lab has previously employed in-situ IR spectroscopy to characterize 2:1, 3:1, and 4:1 solution structures under catalytic conditions. These insights have played a critical role in our understanding of catalyst behavior in carbonyl-containing systems, allowing us to describe byproduct inhibition in the carbonyl-olefin metathesis mechanism. The research presented in …

Data-Driven 2d Materials Discovery For Next-Generation Electronics, Zeyu Zhang

Dissertations

The development of material discovery and design has lasted centuries in human history. After the concept of modern chemistry and material science was established, the strategy of material discovery relies on the experiments. Such a strategy becomes expensive and time-consuming with the increasing number of materials nowadays. Therefore, a novel strategy that is faster and more comprehensive is urgently needed. In this dissertation, an experiment-guided material discovery strategy is developed and explained using metal-organic frameworks (MOFs) as instances. The advent of 7r-stacked layered MOFs, which offer electrical conductivity on top of permanent porosity and high surface area, opened up new …

Computational And Experimental Investigation Of Elemental Sulfur And Polysulfide, Jyoti Sharma

Dissertations

Petroleum processing results in the generation of significant quantities of elemental sulfur (S₈), leading to a surplus of sulfur worldwide. Despite its abundance and low cost, the use of sulfur in value-added organic compound synthesis is limited due to its unpredictable and misunderstood reactivity. This dissertation aims to address this issue by tackling it from two angles. Firstly, by utilizing Density Functional Theory (DFT) calculations, the reactivity of sulfur in the presence of nucleophiles is studied. This facilitates the identification of organic polysulfide intermediates that can be generated under different conditions, as well as the corresponding reactivity for …

High Resolution Intracavity Laser Absorption Spectroscopy Of Transition Metal-Containing Diatomic Molecules, Kristin Bales

Dissertations

Three transition metal-containing diatomic molecules have been studied using intracavity laser spectroscopy. Many of the transitions were recorded using a Fourier-transform spectrometer for detection, allowing collection at Doppler-limited resolution for the gas phase molecules. Several vibrational bands in two electronic transition systems of tantalum fluoride (TaF) have been analyzed, and new molecular constants provided. Transitions involving six electronic states of tungsten sulfide (WS) have been analyzed, with new and updated constants provided, including a deperturbation analysis of three vibrational bands in two of the states. Finally, a fresh perspective on two electronic states of tungsten oxide (WO) included a deperturbation …

Gold(I)-Hydroarylation In Polymer Modification – Alkynes And Alkenes With Unexpected Reactivity, Samuel B. Hunt

Dissertations

Polymer modification is crucial for developing new properties and materials from recalcitrant waste polymers. Synthetically, polymers possess a chemical inertness that renders their functionalization challenging. Specifically, the omnipresence of C–H bonds in all commercial polymers endows their chemical resistance. Thus, developments in C–H activation chemistry are crucial to polymer diversification processes and allow for fundamental insight into the role of material processing conditions on novel chemical reactions. Au(I)-chemistry has recently come to the fore owing to a unique chemical reactivity nonexistent with other transition metals. The alkynophilicity of Au(I), in tandem with their insensitivity to common polymer processing conditions (air, …

Development Of Graphene And Graphene Derivative Advanced Functional Additives: Mechanism And Application In Asphalt Formulations And Thermal Interface Management Materials, Dana Pinson

Dissertations

The overarching focus of my research is the use of graphene and graphene derivatives to enhance polymer properties. My first focus area was the prevention of oxidative degradation of asphalt through the incorporation of a graphene oxide (GO) -based nanoparticle filler to enhance oxygen barrier properties. Primary amine terminated polyisobutylene was synthesized via cationic polymerization followed by post polymerization chain end modification in a range of molecular weights and covalently grafted via the primary amine to graphene oxide aerogel (aGO) to create a polyisobutylene grafted graphene oxide (PIB-g-GO) nanoparticle. PIB-g-GO was then mixed into a substitute asphalt matrix at various …

Synthesis, Characterization, And Photocatalytic Activity Of Photoactive Mofs And M-Hof Under Simulated Visible Light Irradiation, Lamia Ali Siddig

Dissertations

The increasing global energy demand has resulted in environmental issues, leading to a shift in research towards sustainable and renewable energy sources. Among these, solar energy is the most abundant natural resource available. One of the most profitable ways to utilize sunlight is through chemical transformation using photocatalysts. In this regard, we reported the synthesis of different stable porous materials, such as metal-organic frameworks (MOFs) and metal hydrogen-bonded organic frameworks (M-HOFs). The MOF photocatalysts are bismuth-gallate (Bi-gallate), a mixed ligand manganese-based MOF (Mn^II₃(tp)_6/2(bpy)₂. (dmf)) and a new hexagonal layer manganese MOF compound named …

Bismuth And Lanthanides In Mixed Metal Oxides To Metal– Organic Frameworks: Synthesis, Cherectarization, And Photocatalytic Performance, Reem H. Alzard

Dissertations

Known as rare–earth elements (REE), lanthanides (Ln) found in f–blocks of the periodic table, have gained much interest because of their unique characteristics including magnetism, photoluminescence and catalysis. Having a diverse range of coordination geometries, lanthanides can result in different complexes and materials. Herein, three classes of materials containing selected lanthanides such as lanthanide bismuth mixed metal oxides (Ln–Bi oxides), 1D lanthanide coordination polymers (Ln–CPs) and lanthanide metal–organic frameworks (Ln–MOFs) were investigated. Simple route sol– gel method was used to prepare Ln–Bi oxides while Ln–CPs and MOFs were prepared by solvothermal condition. The materials were characterized using multiple analytical, spectroscopic …

V-Shaped Temperature Dependences And Pressure Dependence Of Elementary Reactions Of Hydroxyl Radicals With Several Organophosphorus Compounds, Xiaokai Zhang

Dissertations

Organophosphorus compounds have brought increasing attention since they are widely used as flame-retardants, which can take effect in combustion via reactions with reactive radicals. These reactions are influenced by variables such as temperature and pressure, resulting in a temperature and pressure dependent rate constant. Studying this reaction kinetics has great importance in both combustion reaction and atmospheric environment.

This study is focused on kinetics of several elementary reactions of combustion importance. The kinetics of hydroxyl radicals were studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 295 - 837 K temperature range and the 1 - …

Design, Synthesis, Biological And Computational Studies Of Flavonoid Acetamide Derivatives, Daniel Kasungi Isika

Dissertations

Flavonoid compounds (FC) have extensive biological applications through potent antimicrobial, anti-inflammatory, anticancer, antidiabetic, and antioxidant properties. These applications are nevertheless limited by low bioavailability, poor aqueous solubility, enzymatic degradation, rapid metabolism, and fast body clearance. FC show unique structure-activity relationships (SARs) essential in assessing and mitigating the prevalent challenges impeding their applications. These challenges can be addressed by structural modification of the FC through functionalization of the phenolic rings, modification of the ketone group, and modification of the phenolic hydroxyl groups with bioisosteres.

The objectives of this work are to (i) design and synthesize novel flavonoid acetamide derivatives (FADs) and …

The Influence Of Diamine Curing Additives On The Network Architecture Of Phthalonitrile Thermosetting Polymers, Tyler J. Richardson

Dissertations

Phthalonitrile monomers undergo diamine-promoted polymerization by a complex reaction mechanism involving two competitive cure pathways, forming two primary network architectures: linear polyisoindoline chains and branched triazine crosslinks. The influence of the diamine curing additive on the polymerization pathway, and the influence of the resulting network architectures on cured network properties, have not been adequately explored within the phthalonitrile field. Two structurally different diamine curing additives, bis[4-(3-aminophenoxy)phenyl] sulfone (mBAPS) and 1,3-phenylenebis((4-(4-aminophenoxy)phenyl)methanone) (AEK-134), were studied for the polymerization of resorcinol phenylphosphate phthalonitrile (RPPhPN), where the influence of diamine structure and concentration on the polymerization behavior, network architecture, and bulk thermal and thermomechanical …

Synthesis And Evaluation Of Biologically Active Phosphorous Heterocycles And Lipid A Antagonist Compounds, Saroj Kafle

Dissertations

Cyclophostin and cyclipostins are naturally occurring organophosphates with common structural core units and different phosphate ester substituents. Cyclophostin is a cyclic phosphate triester with a chiral center at phosphorous and C-3a carbon atom while the cyclipostins have characteristic alkyl substituents with varying chain lengths at the phosphate center. Long-chain substituted monocyclic phosphate (2b) and phosphonate (2a) analogs of cyclophostin and cyclipostin are promising inhibitors against serine hydrolases acetylcholinesterase with an IC₅₀ in the nanomolar range.

Biologically active β-lactones and lactams owe their activity, in part, to ring strain. The ring opening of β-lactones and lactams …

Development Of Innovative Multi-Drug Approaches To Counteract Illicit Drug Abuse In The Uae Population, Manal Ali Alhefeiti

Dissertations

The abuse of addictive substances is on the rise in the United Arab Emirates (UAE) population. Consequently, the UAE government spends about Dhs 5.5 billion annually on the rehabilitation of drug addicts. Blood, urine, and hair tests can reveal signs of sporadic or chronic drug use. Given the list of banned chemicals in the UAE, our main objective in this work was to develop a novel analytical method to identify and measure banned substances, especially prescription and over-the-counter drugs in the UAE. We developed and validated a rapid, sensitive and reliable liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) approach for the targeted …

Nano-Supported Biocatalysts For Efficient Wastewater Remediation, Khadega Abobaker Al-Maqdi

Dissertations

The existence of various bioactive organic pollutants in wastewater and municipal water sources has raised concerns regarding their potential effects on human health. As a result, different techniques are being explored to effectively break down these persistent organic pollutants. Peroxidases have recently emerged as a new approach to remediation that may have advantages over traditional methods. However, evaluating the effectiveness of different peroxidases in breaking down various emerging pollutants can be time-consuming and difficult. In this study, a quick and reliable method was developed to test the degradability of 21 emerging pollutants by five different peroxidases (soybean peroxidase, chloroperoxidase, lactoperoxidase, …

Design And Fabrication Of Single-Chain Nanoparticles, Vitrimers, Bottlebrush And Comb Polymers, Logan Dugas

Dissertations

The introduction of novel dynamic exchange chemistries into polymer chains and networks has shown great potential of giving next generation polymeric materials. Within the scope of this thesis, dynamic chemistry is employed to realize single-chain nanoparticles, vitrimer networks, bottlebrush and comb polymers. CHAPTER I provides a broad introduction to the topics at hand, focusing upon the techniques utilized to achieve such materials with relevant literature and understanding of the techniques and architectures explored. CHAPTER II focuses upon the synthesis of single-chain nanoparticles via a copolymerization of polyisobutylene macromonomers with norbornene monomers equipped with pendant anthracene moieties. Through this work, the …

The Synthesis, Characterization, And Utilization Of Functionally Diverse Romp-Based Bottlebrushes, Cheyenne Liu

Dissertations

Bottlebrush polymers have garnered interest in many disciplines for their unique structure-property characteristics and potential applications. These polymers typically exhibit extended rodlike conformations as a result of sterically crowded side-chains. Further, extensive work has focused on expanding the synthetic toolbox for these systems, resulting in excellent molecular weight control, diverse functional group utility and corresponding stimuli-responsive behaviors. This dissertation examines both synthetic and stimuli-responsive tools in the context of bottlebrush systems.

A broad overview of bottlebrush characteristics, synthesis, and applications is discussed in CHAPTER I. CHAPTER II focuses on the use of a chain-transfer agent in the ring-opening metathesis polymerization …

Magnetic Interactions In Open-Shell Conjugated Polymers, Michael Steelman

Dissertations

Most materials are closed shell in which every electron participates in a bond, resulting in unremarkable magnetometry signatures and functionalities. While rare, modern technologies rely on magnetic materials in which unpaired electrons are localized to inorganic atomic centers. In recent decades, a collection of organic open-shell π-conjugated molecules have shown magnetic ordering, albeit at exceedingly low temperatures; a result of weak noncovalent intermolecular interactions limiting long range electronic exchange. Thus, practically applicable sp orbital magnetism that persists at or above room temperature remains a grand challenge for chemistry and physics. Despite the wide variety of chemical structures afforded by organic …

Method Development For The Quantification Of Heavy Metals In Biological Matrices And Its Application To Clinical And Environmental Samples, Michelle Catherine Gende

Dissertations

A three-fold approach was taken to develop a method for the detection of heavy metals in different matrices and had to be performed sequentially. The first was to develop a method capable of quantifying lead in complex matrices by graphite furnace atomic absorption (GFAA). The developed method needed to meet specific analytical requirements, namely, to be robust, sensitive, and accurate. Initially, four different sample preparation methods were explored for the quantification of lead using Escherichia coli (E. coli) as a sample matrix. The sample preparation procedures attempted were acidic dilution, matrix modification, conventional heating digestion, and microwave assisted acid digestion …

Design And Synthesis Of Novel Antibiotics And Anticancer Agents Targeting Pharmaceutically Relevant Enzymes, Sebastian Flieger

Dissertations

Boron neutron capture therapy (BNCT) is a binary radiotherapeutic modality for cancer treatment, in which delivery agents containing 10B atoms are transported into tumor cells and then irradiated with low-energy thermal neutrons. Matrix metalloproteinases (MMPs) are a family of zinc-dependent endopeptidases that are involved in the remodeling and degradation of all components of the extracellular matrix (ECM). Overexpressed levels of MMP activity have been implicated in several disease states including tumor growth and metastasis. We have appended a borane-rich carborane cluster onto MMP-targeting pharmacophores to enable delivery of 10B atoms to a tumor. Herein, we describe the molecular docking experiments …