Chemistry Commons^™

Tailor-Designed Oxalic Acid-Crosslinked Poly(Vinyl Alcohol)/Chitosan Biodegradable Films For Active Food Packaging Applications, Reem Hazem Fathy Anwar Elaasar

Theses and Dissertations

Food packaging plastic waste is posing great threats to ecosystems, human health, and the planet's overall sustainability; therefore, research has been directed towards the fabrication of biodegradable food packaging materials. In this study, active and biodegradable oxalic acid (OA) crosslinked poly(vinyl alcohol) (PVA)/chitosan (CS) composite films of different weight ratios were synthesized via the solvent casting technique and their food packaging properties were investigated. Owing to its water resistance and antibacterial superiority, the composite film with the ratio of OA chemically crosslinked PVA/CS 80:20 was elected to be coated with green tea extract (GTE) to ameliorate its antibacterial and antioxidant …

Mechanism Of Napthenic Acid Binding To Dissolved Organic Matter, Clarissa Jules

Theses and Dissertations

The oil sands in Alberta, Canada are being destroyed by oil extraction because remediation methods have proven largely ineffective. One toxic byproduct of oil extraction is a family of cyclical surfactant organic acids known as naphthenic acids (NAs). They are toxic to aquatic life, including fish, frogs, and aquatic birds. It is suspected that NAs bind to humic acid, a major organic component of soil, in dissolved organic matter in natural water, making them difficult to remove by conventional remediation methods. This problem prompts the following question: what is the binding mechanism between NAs and humic acid when dissolved in …

Protein-Metal Interactions Of A-Synuclein And Bioactive Transition Metals Via Molecular Dynamics, Gonzalo R. Vazquez

Theses and Dissertations

Parkinson’s Disease (PD) is a neurodegenerative movement disorder which has been found to target the dopaminergic neurons of the substantia nigra. It is characterized by the formation of masses known as Lewy Bodies, formed by aggregates of the intrinsically disordered protein (IDP) -synuclein (asyn). Research suggests that alpha synuclein can undergo aggregation in the presence of heavy metals, which may accumulate in the body through a variety of mechanisms. To study how metals may play a role in wildtype (WT) asyn aggregation, MD simulation of the protein was performed in the presence of bioactive transition metals including Fe2+, Fe3+, Cu+, …

Electrochemical And Conformational Patterns Of S-Glycosides And The Synthesis Of Schistosoma Mansoni Antigens, Bhavesh Rajendra Deore

Theses and Dissertations

This thesis dives into two relevant fields in carbohydrate science: reactivity and conformation. We centered our attention on S-glycosides, a common class of glycosyl donors and glycomimetics, to study the influence exerted by the structural architecture over the conformational properties about flexible bonds and the reactivity towards electrochemical activation. Studying the conformational properties of sugars is key to understanding the molecular recognition mechanisms underlying their biological functions. Moreover, a well understanding of how the molecular components affect free rotation about bonds can be valuable information to design improved glycomimetic drug candidates. On the other hand, electrosynthesis is a promising application …

Synthesis And Characterization Of Novel Coumarin Derivatives, Jeanmeil M. Nestor

Theses and Dissertations

An optimized approach toward the synthesis of representative coumarin derivatives is described. In addition to standard heat application methods, microwave-assisted coupling has proven beneficial in generating the targeted molecular hybrids which will serve as key templates in the development of new drugs to address resistance and specificity challenges. The coumarin moiety is a fantastic scaffold for molecular hybridization and has gained much warranted attention due to its efficacy in anticancer, antibacterial, and antitumor activity. In this research, novel molecular hybrids of umbelliferone were synthesized and fully characterized as new potential players in the anticancer, antitumor and antibiotic race, as well …

Adsorption And Recovery Studies Of Cadmium And Lead Ions Using Biowaste Adsorbents From Aqueous Solutions, Liang Feng

Theses and Dissertations

The use of low-cost biowaste adsorbents for the removal of toxic metal ions from aqueous solutions offers significant environmental benefits and demonstrates strong potential. This study evaluated luffa peels and chamomile flowers as low-cost biosorbents for the adsorption and recovery of Cd2+ and Pb2+ ions in both batch and column modes. To enhance adsorption capacity, the biosorbents were treated with 0.4 M HNO3 or 0.4 M NaOH. Fourier transform infrared spectroscopy (FTIR) characterization showed that surface OH, C=O, CO and COO groups played a role in the adsorption process. Batch adsorption studies indicated an order of adsorption capacity as follows: …

Biological And Chemical Evaluation Of Amide-Based Cjoc42 Derivatives As Potential Gankyrin-Inhibitors For The Treatment Of Breast, Lung, And Liver Cancer, Benita Britton-George

Theses and Dissertations

Gankyrin is an ankyrin-repeat protein overexpressed in certain cancers and is responsible for cell growth and proliferation. Gankyrin is important to the development of many types of cancer, including breast, lung, and liver cancer. Consequently, gankyrin and its various protein-protein interactions, are prospective therapeutic targets for inhibiting the progression of certain cancers. In 2016, the first small molecule inhibitor of gankyrin, cjoc42, was discovered and subsequently demonstrated modest antiproliferative activity against liver cancer cells. Previous work from our lab demonstrated that replacing the sulfonate ester of cjoc42 with an amide group significantly improved gankyrin binding while enhancing antiproliferative activity against …

Investigation Of The Binding Mechanisms Between Naphthenic Acids And Humic Acid Using Raman Spectroscopy And Computational Modeling, Jaelyn N. Palmer

Theses and Dissertations

The oil sand regions in Alberta, Canada have proven to be costly to the environment despite its economic benefits. The toxins produced during oil processing are sent to tailing ponds to be recycled, though often leaking into nearby waterways and soil. Naphthenic acids, NAs, are one of the most common toxins produced and have shown to be toxic to aquatic life, animals, and humans. As there is dissolved organic matter in tailing ponds and surrounding environments, tailing ponds often lead to NAs coming in contact with organic material. Humic acid, HA, is a major soil component that has been suspected …

Qualitative Analysis Via Network Models Of Human Dynamin-1 Throughout Gtp Hydrolysis, Kevin Brian Schulman

Theses and Dissertations

This thesis aims to elucidate the molecular mechanisms by which nucleotide binding dictates the intrinsic dynamics and to understand the functional conformational changes of Human Dynamin-1 during the GTP hydrolysis cycle through the use of Elastic Network Models (ENM). A comprehensive understanding of this process is crucial given dynamin's role in clathrin-mediated endocytosis (CME). The research utilized both experimentally derived crystal structures and AlphaFold-predicted structures of dynamin, specifically examining the GTPase and Bundle Signaling Element (BSE) domains across nucleotide-free, GTP-bound, GDP-bound, and transition states. The essential features of the research methodology involved a multi-scale computational approach. Qualitative analyses were performed …

Purification Of Recombinant His6-Gfp-Preptin Fusion Protiens, Apoorva Kollaram

Theses and Dissertations

Preptin, a 34-amino-acid peptide derived from proinsulin-like growth factor II, has emerged as a promising therapeutic candidate for both Type 2 diabetes mellitus and osteoporosis. Its dual functionality—stimulating insulin secretion without inducing hypoglycemia and promoting osteoblast proliferation—positions it as a unique alternative to traditional sulfonylureas and osteogenic agents. In this study, we developed a purification protocol for green fluorescent-preptin fusion proteins. These fusion proteins will be used to investigate the functional significance of residues Pro17, Val18, Gly19, Trp27, Lys28, and Gln29 in rat preptin, which shares high sequence similarity with the human form. Site-directed mutagenesis was performed using NEB Q5 …

Synthesis Of Novel Schiff Bases And Their Metal Complexes, Ryan J. Lukkarinen

Theses and Dissertations

Presented in this thesis is the synthesis and characterization of multiple thiosemicarbazones and dithiocarbazates, as well as their corresponding metal complexes. Chapter 1 is an introductory chapter exploring the significance and potential applications of this work. Chapter 2 focuses on thiosemicarbazone synthesis and characterization. Chapter 3 describes the synthesis and characterization of dithiocarbazates. Chapter 4 details metal complex synthesis using the previously described ligands. Chapter 5 summarizes the conclusions of the research and future work that may stem from it.

High Throughput, Solid Sample Analysis With Cone-Based Mass Spectrometric Ionization Sources, Emily J. Wiggins

Theses and Dissertations

The widespread presence of environmental and consumer-product contaminants (e.g. trace metals, opium alkaloids) has underscored the need for rapid, reliable, and high-throughput analytical techniques that are capable of handling complex solid samples. While traditional mass spectrometric (MS) methods tend to have high sensitivity and accuracy, they often require labor-intensive and time-consuming sample preparation steps that limit throughput and field applicability. This thesis investigates the use of 3D-Printed Cone Spray Ionization-Mass Spectrometry (3D-PCSI-MS) as an ambient ionization technique for the direct screening of contaminants from solid matrices, eliminating the need for traditional sample preparation and allowing for real-time analysis.

In …

Modification Of Nanoparticles For Designed Interfaces, Tony Lee Neely, Jr.

Theses and Dissertations

The work contained herein, is focused on the design, synthesis, and characterization of polymer nanocomposite interfaces and the property enhancement afforded from said interface design. Through the use of reversible addition fragmentation chain transfer (RAFT) polymerization for the grafting of polymer chains to silica nanoparticles, the surface of silica nanoparticles can be manipulated to tune the properties of the nanocomposite as a whole.

In the first part of this work, heterogeneity is introduced onto the surface of silica nanoparticles via a sequential RAFT polymerization to afford a bimodal brush system. A densely grafted, short brush population is polymerized from the …

Unraveling The Reactivity Of Nitrate Ester Explosives: Insights From Femtosecond Time-Resolved Mass Spectrometry And Computational Chemistry, Erica Britt

Theses and Dissertations

This dissertation uncovers the ultrafast molecular mechanisms underlying the decomposition of nitrate ester explosives—nitroglycerin (NG), ethylene glycol dinitrate (EGDN), and amyl nitrate—through the integration of femtosecond time-resolved mass spectrometry and advanced computational chemistry. Although these compounds play fundamental roles in both military and civilian contexts, the precise molecular dynamics governing their pronounced reactivity and impact sensitivity have remained inadequately characterized. Our research establishes that low O–NO2 bond dissociation energies are the primary driver of ultrafast fragmentation and high reactivity in all three esters. The distinctive molecular architectures of these esters dictate their explosive properties: NG’s tri-nitrate configuration leads to exceptional …

Facile Synthesis Of Gold, Copper, And Silicon Nanostructures By Laser Ablation In Liquid, Nicholas Simpson

Theses and Dissertations

Metal nanoparticle (NP) synthesis is a continually evolving area of research, owing to the widespread application of NPs in fields such as catalysis, drug delivery, and biosensing. Compared to bulk metal material, NPs contain a larger proportion of surface atoms and exhibit unique optical properties, thus making them ideal for applications where maximizing surface interactions is key. Moreover, their compositions can be altered in several different ways, as evidenced by metal alloy, core/shell, supported, and defective NPs. While conventional synthesis methods are capable of producing NPs in large quantities, they often require conditions of high temperature and pressure, strong reducing …

Development, Synthesis And Characterization Of Advanced Low- Cobalt And High-Nickel Cathode Materials For Lithium-Ion Batteries, Arjun Patel

Theses and Dissertations

This dissertation focuses on the improvement of structural and electrochemical stability of active materials for lithium-ion batteries. It explores the modification strategies to mitigate the issues related to Ni-rich cathode materials, along with the continuous production of cathode precursors using a slug flow reactor to improve the quality of the product.

The First part of the dissertation examines the effect of substitution of cobalt with aluminum and iron on the electrochemical stability of Ni-rich lithium nickel cobalt manganese oxide (NCM) materials. This study investigates how Al and Fe doping work and how they impact the performance and stability of these …

The Development Of A One Pot, Two Reaction Synthetic Preparation Of 1,2,4-Oxadiazole, And Synthesis Of Ataluren, A Novel Drug In The Fight Against Duchenne Muscular Dystrophy. Efforts Towards The Synthesis Of A Potential Protease Inhibitor Against The Main Protease (3clpro) Of Covid-19, Austin J. Carter

Theses and Dissertations

1,2,4-Oxadiazoles are five-membered heterocyclic structures first synthesized by Tiemann and Krüger in 1884. Recent discoveries suggest an array of useful biological properties.In preparation of 1,2,4-oxadiazoles, the most prevalent precursors are amidoximes, which can be created via the reaction of nitriles with hydroxylamine hydrochloride and a base. The amidoximes are reacted with an activated carboxylic acid to yield an acylated intermediate. This intermediate can be exposed to a base to cyclize into the 1,2,4-oxadiazole. This thesis describes the efforts in combining these three steps into a unified one-pot synthesis.

Currently, there are a significant number of commercially available FDA approved and …

Asymmetric Synthesis Of The Hiv Protease Inhibitor Tmc-126 And An Anti-Malarial Agent Via A Titanium Tetrachloride Mediated Asymmetric Glycolate Aldol Addition Reaction. Redefining The Curtius Rearrangement Reaction Via Dehomologation Of Carboxylic Acids Bearing Alpha-Leaving Groups, Kweku Amaning Affram

Theses and Dissertations

Acquired Immune Deficiency Syndrome (AIDS) and malaria are two devastating infectious diseases caused by HIV and Plasmodium parasites. AIDS is caused by HIV-1 and HIV-2, transmitted through sexual contact, blood transfusions, needle sharing, and perinatal routes. Malaria, caused by plasmodium parasites through mosquito bites. Today, millions of people around the world have been infected with HIV and malaria and much research has been done to treat it. However, despite advancements in therapeutic options, these diseases remain a significant global health threat, particularly in developing countries due to the emergence of drug-resistant strains for both HIV and malaria complicating eradication efforts. …

Site-Specific Modification Of Antibodies Utilizing Microbial Transglutaminase For Improved Immunoassay Performance, Emily Beitello

Theses and Dissertations

Immobilization strategies used for fixing antibodies to solid phase surfaces significantly contribute to the antigen capture capacity and influences the performance and sensitivity of immunoassays. Traditional methodologies result in the random orientation and/or the weak attachment of immobilized antibodies. Different formats of immunoassays scope in applicability to many fields of research and everyday use. Improving the efficiency of immobilizing antibodies in immunoassays is a beneficial endeavor to increase assay sensitivity. Here, we investigated the use of enzyme-mediated conjugation of antibodies to facilitate a highly oriented immobilization. Microbial transglutaminase (mTG) catalyzes the covalent bond formation between a plethora of primary amine …

Synergistic Adsorption Of Pb (Ii) From Aqueous Solution Using Calcined Biochar-Bentonite Clay Hybrid, Azeezat Faderera Abdul-Raheem

Theses and Dissertations

The biochar-bentonite clay hybrid was prepared by coprecipitation with the goal of producing a material that can remove Pb (II) from aqueous solutions effectively. Incorporating bentonite clay onto the Douglas fir biochar (DFB-BTC) surface significantly improved the adsorption capacity by introducing more active sites, strengthening the structural properties, and promoting strong adsorbate interactions. The point of zero charge of the adsorbent was slightly higher than that of the pristine DFBC. All sorption experiments were performed at pH 5, and the system obeyed the Langmuir adsorption isotherm. The highest Langmuir adsorption capacities observed at 298, 308, and 318 K were 48, …

Impact Of Cascading Optical Processes On Spectroscopic Quantification Of Absorption And Scattering Properties Of Samples, Pathum Dilshan De Silva Wathudura

Theses and Dissertations

Light absorption and scattering are fundamental properties of matter, particularly significant in nanoscale materials. This study explores how cascading optical processes affect the experimental measurement of absorption and scattering intensities, along with scattering depolarization, in samples containing absorbers and scatterers. The experimental UV–vis spectrum results from the combination of absorption and scattering extinction spectra. However, the maximum measurable extinction may be limited by forward scattered light. Light absorption decreases the intensity of scattered light and influences scattering depolarization. While scattering can reduce absorption along the optical path to the detector, sufficient absorption of the scattered light may counterbalance this effect, …

Engineering Functionalized Nanomaterials For Targeting And Ablating Biofilms On Surfaces, Dhanush Lakmal Yapa Amarasekara

Theses and Dissertations

Biofilms on both the surface and interior of medical devices pose major challenges, including hindering device performance and serving as infection sources. These biofilms form a protective layer around bacteria, shielding them from the body’s immune system and antibiotics. This makes infections difficult to treat, as the bacteria within the biofilm are resistant to both antibiotics and immune defenses. Additionally, biofilms can induce inflammation and irritation in nearby tissues, leading to further health complications. Antibiotic resistance raises concerns about the emergence of multi-drug resistant (MDR) pathogens. MDR infections are difficult to treat, leading to prolonged hospital stays and the need …

Biothermodynamics Of Metal And Dna Coordination To The Pneumococcal Transcription Factors Adcr, Scza, And Copr, Alexander James Cutright

Theses and Dissertations

ransition metals are micronutrients that play critical roles in all forms of life, acting as stabilizing ions, catalytic centers, and as signaling ions. Due to their importance, classes of biomolecules have been designed with the sole purpose of regulating their intracellular concentrations. One group of which are transcription factors, which regulate intracellular metal concentration by activating or repressing transcription, dependent on metal availability. The activation of transcription factors by metal availability can be attested to conformational changes that are governed by both dynamics and thermodynamics. Due to the influential nature of transcription factors, their activity and activation mode have become …

Density Functional Theory And Machine Learning Analysis Of C—C Reductive Coupling From Terminal Cyanido And Cyaphido Complexes, Roberto Magdiel Escobar

Theses and Dissertations

Carbon–carbon (C–C) bond activation has gained increased attention as a direct method for the synthesis of pharmaceuticals and industrial chemistry. Due to the thermodynamic stability and kinetic inaccessibility of the C–C bonds, however, activation of C–C bonds by homogeneous transition-metal catalysts under mild homogeneous conditions is still a challenge. Most of the systems in which the activation occurs either have aromatization or relief of ring strain as the primary driving force. The activation of unstrained C–C bonds of phosphaalkynes does not have this advantage. This study employs Density Functional Theory (DFT) calculations using the Gaussian16 package to elucidate and compare …

Evaluation Of Polymerization Condition Reactions Of Methyl Vinyl Ketone For Hydrogen Storage, Rituborna Ghosh

Theses and Dissertations

Hydrogen is widely regarded as one of the most promising clean alternative fuel sources; however, its widespread adoption has been hindered by significant challenges related to storage and transportation. Various storage methods have been proposed and developed, with continuous advancements being made to address these issues. Among the most effective solutions is the utilization of polymers, which serve as safe and efficient hydrogen storage media. This work investigated the polymerization of methyl vinyl ketone using different ratio of monomer: initiator and monomer: crosslinker using N,N′-methylenebisacrylamide (MBA) as crosslinker and ammonium persulfate (APS) as initiator in a free radical polymerization mechanism. …

Machine Learning Optimized Depolymerization Of Pet (Polyethylene Terephthalate) Via Glycolysis, Mehwash Aamir

Theses and Dissertations

Over 90% of the approximately 1 million PET bottles sold every minute end up in landfills or oceans, where they can persist for centuries. Plastic pollution urgently needs sustainable management and recycling solutions to mitigate the environmental impact of PET waste. From all techniques to recycle plastic waste, catalytic glycolysis stands out for its rapid reaction time, high monomer yields, lower costs, and enhanced durability.

In this work glycolysis of PET was evaluated under microwave conditions using 1,5,7-Triazabicyclo [4.4.0] dec5-ene (TBD) and 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU) as catalysts, being DBU as the best catalyst for further analysis. The effect of …

Microwave-Assisted Green Synthesis Of Spiroindolinopyranopyrazoles, Esther Owusu

Theses and Dissertations

Green Chemistry, usually known as sustainable chemistry, is widely implemented worldwide to safeguard human health and the environment. Recent investigations in organic synthesis and chemical transformation have demonstrated that green chemistry techniques are significantly reducing both chemical waste and reaction time. In order to fulfill this ecological requirement, it is crucial to lessen the utilization of perilous solvents and noxious chemicals, while also creating innovative reaction methods that decrease the production of trash. The implementation of such methodologies can greatly enhance the field of green chemistry. A more environmentally friendly synthetic method was utilized to generate spiro chemicals and their …

Synthesis Of Photocleavable Molecules For Neurological Applications, Nishal Madujith Egodawaththa Arachchilage Don

Theses and Dissertations

In recent biomedical research, the precise control of molecular dynamics through light activation has emerged as a powerful tool, particularly in the field of neurobiology. This approach involves the use of photocleavable cages or photoprotective groups (PPGs) that are chemically tethered to biologically active molecules such as neurotransmitters or calcium chelators. These cages remain inert until exposed to specific wavelengths of light, typically in the visible range, triggering the release of the active compound with high spatiotemporal precision.

For neurotransmitter systems, such as glutamate (Glu), which plays a critical role in synaptic transmission and memory formation, researchers have developed novel …

Novel, Ultra-Fast Electrochemical Sensors For The Enhanced Detection Of Neurotransmitters And Toxic Heavy Metals In Aqueous Solutions, Noel Manring

Theses and Dissertations

Neurodegenerative diseases (NDDs) are a growing global health concern, affecting millions of people worldwide. NDDs arise from the progressive loss of neuronal cell function, ultimately leading to cell death. Abnormal levels of neurotransmitters, the chemical messengers in the brain, have also been linked to NDDs. Despite various treatments and medications aimed at alleviating physical and mental symptoms, there is currently no cure or means to halt disease progression. While the exact pathogenesis of NDDs remain poorly understood, cognitive decline is largely attributed to brain volume reduction, particularly in the hippocampus. Clinical studies suggest that environmental factors, such as exposure to …

Ionic Nanomedicines And Biocompatible Hydrogel: Synthesis, Characterization And Application In Cancer And Drug Delivery, Mujeebat Bashiru

Theses and Dissertations

This dissertation is focused on the development of novel class of ionic materials (IMs), and ionic nanomedicines (INMs) for cancer treatment. These IMs are composed of two therapeutics combined via electrostatic attraction. The impact of various counterions on the drug’s cytotoxic and photophysical properties are unveiled. Moreover, the mechanism of internalization, enhanced toxicity of these materials is investigated by determining their cellular uptake, subcellular localization, and cell death mechanism. Furthermore, the in vivo bioimaging capabilities of the drugs is investigated to validate their potential for clinical relevance. The second part of this dissertation is focused on the synthesis of biocompatible …