Chemistry Commons^™

Detection And Analysis Of Solid-Phase Nutrients In Complex Benthic Cyanobacterium Communities, Cassidy Ann Crandell

Theses and Dissertations

Eutrophication is one of the most serious water quality issues affecting aquatic systems in the United States. Densely populated urban areas as well as mining and agriculture are major sources of anthropogenic nutrient loading into lakes and rivers. Excess loading of nutrients like phosphorus (P) into these ecosystems can cause native algal species to be outcompeted by harmful algal bloom (HAB) species. Increases in these HAB events are a growing public health concern as contact with excreted toxins can be harmful for human, aquatic, and land species. Remediation techniques like total maximum daily loads (TMDLs) have been implemented to reduce …

Impaired Waters: New Treatments And Improved Methods For Pfas And Algae Toxins, Alexandria Forster

Theses and Dissertations

Per- and polyfluoroalkyl substances (PFAS) are high-profile environmental contaminants, many having long persistence in the environment and widespread presence in humans and wildlife. Following phase-out of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in North America and restrictions in Europe, PFAS replacements are now widely found in the environment. While liquid chromatography (LC)-mass spectrometry (MS) is typically used for measurement, much of the PFAS is missed. To more comprehensively capture organic fluorine, we developed sensitive and robust methods using activated carbon adsorption, solid phase extraction, and combustion ion chromatography (CIC) to measure total organic fluorine (TOF) in industrial wastewaters, river …

Molecular And Hybrid Catalysts For Selective Hydrodeoxygenation Of Lignin Model Compounds, Jacob G. Tillou

Theses and Dissertations

Lignin is a highly aromatic, branched polymer and could be utilized as a renewable source of liquid fuel. The advent of “lignin-first” depolymerization processes have allowed for the high-yield isolation of oxygenated aromatic monomers from lignin. These oxygenated aromatic compounds are lower in energy and stability than their deoxygenated counterparts. Selective deoxygenation of these compounds would result in stable, higher value liquid fuels. Using molecular catalysts, selective deoxygenation, or hydrodeoxygenation (HDO), of lignin-derived compounds in the presence of hydrogen is possible.

Immobilization of these molecular catalysts on metal oxide surfaces eliminates the possibility of bimolecular decomposition and allows for easier …

Molecular Rotors For Quantifying Kinetic Effects Of Stabilizing Non-Covalent Interactions, Binzhou Lin

Theses and Dissertations

This thesis describes the development of molecular machines as analytical instruments to measure the strength of non-covalent interactions and to test hypotheses of reaction mechanisms. The first chapter is a review of molecular rotors. The second chapter presents the development of a molecular rotor that can be controlled using electrostatic interactions. Previous examples have used electrostatic interactions to slow down or inhibit molecular motion. Our system is activated and sped up using electrostatic interactions. The third and fourth chapters describe the application of molecular rotors designed to experimentally measure the strength and stability trends for non-covalent pnictogen and chalcogen interactions. …

Electronic Structure Investigation Of Photoswitch-Embedded Organic Frameworks And External Electric Field Effects On Carbon Dioxide, Austin Hill

Theses and Dissertations

Metal- and Covalent-Organic Frameworks (MOFs and COFs, respectively) are chemically versatile systems that have diverse applications, ranging from drug delivery to energy storage. This versatility is due to the highly tunable nature of organic frameworks, which utilize metal clusters, chemically diverse metals, and organic ligands. Researchers have recently demonstrated how MOFs and COFs can be remotely tuned through the use of photochromic organic linkers and light (Martin, et al., 2022). The implications of these findings are significant and have numerous applications, primarily in optical switching and energy storage. However, the photochromic mechanism within the organic framework must be investigated, which …

Optimizing The Protein Yield Of The Collagen Mimetic Peptide: Col108, Fahmida Akter

Theses and Dissertations

Abstract

The fibril-forming collagen mimetic peptide Col108, produced in E. Coli, has shown potential for innovative biomaterial applications. However, further research is constrained by its limited yield. My study aims to enhance the experimental parameters and has successfully pinpointed rifampicin as an efficient method to boost the production of Col108.

Synthesis And Characterization Of Medicinally Privileged Aza Heterocycles, Nneoma James

Theses and Dissertations

Four-membered cyclic amides, commonly known as β-lactams, have played a crucial role in drug discovery research since its discovery by Alexander Fleming in 1928 from Penicillium notatum. The β-lactam antibiotics are broadly effective against several bacterial infections through acylating the transpeptidase involved in cross-linking peptides to form peptidoglycan or periplasmic murein, which is a fundamental constituent of the bacterial cell wall for both the gram-positive (ten or more layers) and gram-negative (one or two layers) bacteria. Although for more than eight decades, β-lactams have been recognized as antibiotics, later, other medicinal activities of β-lactam derivatives have been reported, including lowering …

Chemical Investigation Of The Ethanol Extract Of Tillandsia Usneoides (Spanish Moss), Jakir Hossain

Theses and Dissertations

Tillandsia usneoides in epiphytic bromeliads takes up water through absorptive trichomes on the shoot surface under extreme environmental conditions. Although previous studies revealed the way by which T. usneoides absorbs water and prevents water loss, its water transport remains unclear. Uses of T. usneoides L. have been documented going back to pre-Columbian and late archaic societies. Between the 1800s and 1900s. T. usneoides was utilized in fruit packing and polish, among other industrial goods. In terms of medicine, tillandsia is well-known for treating leucorrhea, rheumatism, ulcers, hemorrhoids, and as an anti-diabetic, emetic, analgesic, purgative, antispasmodic, and diuretic. The chemical composition …

La1-Xsrxcoo3 Perovskite: Antimicrobial Properties And Pvdf Based Piezoelectric Nanogenerator For Energy Storage Through Self-Induced Polling, S M. Anyet Ullah Shohag

Theses and Dissertations

Piezoelectric Nanogenerators (PENGs), which can produce electrical energy from mechanical energy via ferroelectric effect, are one of the ambient sources of green energy. PENGs have gathered a huge attention due to cost-effectiveness, mechanical stability, and easy installation process. In this experiment, different weight percent of Sr2+ doped Lanthanum Cobaltite (La1- XSrXCoO3) perovskite, a ferroelectric material, was synthesizes by using a simple combination of sol-gel and molten-salt process and then characterization by X-ray diffraction, and scanning electron microscopy ensures the uniform morphology of nano cubes. Poly (vinylidene difluoride) (PVDF), N,N-dimethylformamide and acetone solution were used to make a flexible film using …

Beta Lactams Anticancer Effect On Human Breast Cancer, Mcf-7 Cell Line, Ailis A. Abalos

Theses and Dissertations

Cancer is a disease where abnormal cells replicate uncontrollably in that same region and/or other parts of the body. One in eight women are diagnosed with breast cancer, thus making it the second leading cause of cancer-related deaths in the U.S. Chemotherapy, is the utilization of medicinal compounds (drugs) to treat cancer. While most are nonspecific and target both cancer and healthy cells, more emphasis is on developing drugs with specificity (only target tumor cells) and low toxicity. Interestingly, Beta Lactams (β-lactams) have emerged as a class of compounds that are effective in the treatment of various cancers. The benefits …

Modulating Covalency In A Ni-H-Al Subunit: Synthesis And Characterization Of A Series Of Electronically Differentiating Ni-Al Heterometallics, Aleida Guadalupe Gonzalez

Theses and Dissertations

Metal hydrides are moieties that are present in a variety of applications as intermediates in catalysis. Despite the vast utilization of metal hydrides, monometallic metal hydride complexes bear limitations in inert-bond activation and functionalization. A strategy to overcome these limitations and access more challenging reactivity is utilizing metal-metal cooperativity on a single platform to further activate hydride moieties. Although incorporating multiple metal centers on a single ligand scaffold has been realized, access to heterometallic hydride-bearing complexes is a greater synthetic challenge. Given the limitations in accessing such systems, the reactivity and electronic structure of heterometallic hydrides are seldom studied. Recently, …

A Deep Dive Into The Conformations Of Fluorine-Substituted Benzoic Acids And Ethanesulfonic Acid And Spectroscopic Characterizations Of Their Hydrogen-Bonded Complexes, Alitza Gianina Gracia

Theses and Dissertations

Microwave spectroscopy is a technique used to study the molecular structures of a wide range of systems. The first part of the thesis focuses on fluorinated benzoic acids and complexes they form through hydrogen bonding to explore the fluorination effect, while the last part shifts to ethanesulfonic acid and its interaction with water. The study of 3,4,5-triflurorbenzoic acid with formic acid offers insight on the proton tunneling process, which is a process that occurs in many chemical and biological processes. Microwave spectroscopy can help provide dynamic information for the better understanding of this fundamental process. Solvation is another topic that …

Improvement Of Triboelectric Nanogenerator By As-Prepared Lithium Niobate For Energy Harvesting And Sensing Applications, Jahid Inam Chowdhury

Theses and Dissertations

One readily available green energy source that is used to address the small-scale energy requirement is mechanical energy. To harvest mechanical energy, supply energy for upcoming electronic devices, and enable flexible health monitoring, triboelectric nanogenerators composed of perovskite and lightweight polymers have garnered significant interest. A material named lithium niobate (LiNbO3) was produced in two different phases and used to make a flexible triboelectric nanogenerator (TENG). Furthermore, lightweight polydimethylsiloxane (PDMS), Polyvinyl Alcohol (PVA), and LiNbO3 nanoparticles were used to produce a small triboelectric nanogenerator that successfully converts mechanical energy into electricity. LiNbO3 nanoparticles were first created and loaded into polydimethylsiloxane …

Study Of Modified Salinomycin Analogs On Inhibition Of Triple Negative Breast Cancer Metastasis And Invasion, Farnaz Malekmarzban

Theses and Dissertations

Triple negative breast cancer (TNBC) is a more aggressive type of breast cancer which contains faster growth, higher metastasis rate and worse prognosis. The main challenge toward treatment of this type of cancer is being heterogeneous. Recently, Salinomycin (SAL) has been considered as a potential agent for triple negative breast cancer treatment. However, chemical modification of SAL is needed to improve SAL selectivity to cations and decrease its cytotoxicity. The purpose of this study was to evaluate the effect of chemically modified analogs of SAL on the viability, metastasis, Wnt pathway as well as angiogenesis of Triple negative breast cancer …

Potent And Selective Small Molecule Mcl-1 Inhibitor Demonstrates Anti-Myeloma Activity And Overcomes Chemotherapy Resistance, Omar Sami Faleh Al-Odat

Theses and Dissertations

Despite a record number of clinical studies investigating various anti-myeloma treatments, the 5-year survival rate for multiple myeloma (MM) patients in the US is only 55%, and nearly all patients relapse. Poor patient outcomes demonstrate that myeloma cells are "born to survive” which means they can adapt and evolve following treatment. Thus, new therapeutic approaches to combat survival mechanisms and target treatment resistance are required. Importantly, Mcl-1, anti-apoptotic protein, is required for the development of MM and treatment resistance. This study looks at the possibility of KS18, a selective Mcl-1 inhibitor, to treat MM and overcome resistance. Our investigation demonstrates …

Implementing 1.5 Millimeter Internal Diameter Columns And A Portable Capillary Column Instrument Into Monoclonal Antibody Analytical Workflows, Benjamin Libert

Theses and Dissertations

Using 1.5 mm inner diameter (i.d.) columns to bridge the gap between routinely used 2.1 mm i.d. columns and capillary bore columns allows for a sequential but significant increase in performance without the need for specialized equipment associated with very low dispersion liquid chromatography (LC) systems. These 1.5 mm i.d. columns balance an increase in sensitivity compared to 2.1 mm i.d. columns (theoretically doubling the time-domain peak area in mass sensitive detectors for the same mass load), while mitigating the efficiency losses due to extra-column dispersion effects that are commonly observed with 1.0 mm i.d. columns. Here, the use of …

Activity Descriptors As Tools For Designing Highly Efficient Electrocatalysts For Water Splitting, Aya Gomaa

Theses and Dissertations

There is an uprising urge to design efficient, active, and durable catalysts to achieve sustainable hydrogen production. The unambiguity of which material should be used pushed the scientific community to devote enormous efforts in exploring different elements with different ratios on trial and error bases. However, the bridge between the theoretical calculation and the experiments introduced a new realm of designing efficient catalysts by introducing the concept of activity descriptors. In the first part of the thesis, the ability to convert waste stainless steel (SS) 316L meshes into highly efficient and durable oxygen evolution reaction (OER) catalysts is demonstrated. The …

Integrated Computational Approaches: Elucidating Molecular Mechanisms Of Pathogenic Proteins And Designing Novel Inhibitors Against Mycobacterium Tuberculosis And Sars-Cov-2, Justin David Carbone

Theses and Dissertations

Chapter 1 introduces computational strategies in computer aided drug design (CADD), focusing on physics-based methodologies to enhance drug discovery. This chapter also discusses the theoretical foundations and practical applications of molecular dynamics (MD) simulations including free energy and stochastic kinetic analysis. In Chapter 2, CADD methods lead to development of inhibitors targeting the RNA Dependent RNA Polymerase (RdRP) of SARS-CoV-2. Inspired by the nucleotide inhibitor Molnupiravir, we aim to design a combinatorial library of 72 novel inhibitors capable of impeding a dual threat inhibition mechanism inducing lethal mutations along with stalling viral replication with specific selectivity to RdRp over Human …

Zinc Oxide Nanostructures Synthesized By Hot Water Treatment For The Photocatalytic Degradation Of Organic Pollutants In Water, Ranjitha Kumarapuram Hariharalakshmanan

Theses and Dissertations

Photocatalysis using nanostructured semiconductors for the degradation of organic pollutants has received significant attention as an advanced water treatment method. A photocatalyst absorbs light with energy greater than or equal to its band gap and generates electron-hole pairs. These electrons and holes take part in redox reactions in water to generate reactive oxygen species, such as hydroxyl radicals and superoxide anions, which can break down organic contaminants. However, this method has some challenges, such as electron-hole recombination, which reduces the efficiency, high cost of nanostructure synthesis, and reduced durability of nanostructured photocatalysts in suspension form. The immobilization of photocatalyst nanostructures …

An Investigation Of The Mindset Context And Its Downstream Effects On Marginalized Student Outcomes In College Stem Courses, Ronia Naim Kattoum

Theses and Dissertations

Multiple national calls centered on critical thinking and social justice have been made to improve and reform higher education in science, technology, engineering, and mathematics (STEM) courses to increase the representation of students from marginalized groups in the STEM workforce and equip all students for success. To help answer this call, our project has two overarching goals: 1) Identify pathways to increase student success in STEM courses at a moderately selective metropolitan institution with a diverse population that can be generalized to similar institutions, and 2) determine how instructional practices influence perceptions of the learning environment, especially for marginalized students. …

Towards Carbon Dioxide Reduction: Synthesis And Characterization Of Ccc-Nhc Pincer Iron Complexes., Joshua Mensah

Theses and Dissertations

The industrial revolution came with its downside of emission of greenhouse gases into the atmosphere. The NOAA reported in 2019 that, of the greenhouse gases emitted into the atmosphere, CO2 contributed to about 80% of the increased greenhouse gases hence the need for CO2 Sequestering and Storage (CSS) and ultimately leading to Carbon Capture and Recycling (CCR) as a viable option to convert CO2 into useful forms. The race to find the best catalyst for CCR has led to the synthesis of many organometallic compounds. Pincer complexes catalyzed CO2 reduction has gained notoriety recently because of the tunability and robustness …

Development Of Chiral Lewis Base Catalysts For Chlorosilane-Mediated Asymmetric C-C Bond Formations, Changgong Xu

Theses and Dissertations

The chiral hydrazine is a crucial structural motif that serves as pivotal structural elements in numerous natural products and biologically significant molecules. We are particularly interested in the catalytic asymmetric reduction of hydrazones, as well as the catalytic asymmetric propargylation and allenylation of hydrazones, because they provide direct pathways to these enantio-enriched chiral building blocks. In this work, we will explore the potential of two different categories of chiral Lewis base catalysts in the said transformations.

Developed by another student in our group, axial-chiral 3,3’-triazolyl biisoquinoline N,N’-dioxides derived catalysts are tested and demonstrated its capability in activating various hydrazone …

Exploring The Potentials Of Delafossite-Coated Cotton Textiles: Photocatalytic Self-Cleaning, Uv-Blocking, Anti Microbial Activity And Hydrophobicity, Shahria Ahmed

Theses and Dissertations

Delafossite materials demonstrate multifunctional applications due to their excellent catalytic properties, which vary depending on their morphology, particle size, and synthetic method. Herein, a few novel applications of the delafossites are reported, which can be implemented in commercial, medical, and domestic settings. In present work we are presenting two different delafossite CuGaO2 and CuFeO2 nanoparticles and its composite with cotton fiber. Multifunctional cotton fabric is prepared by depositing a uniform coating layer of CuGaO2 and CuFeO2, exhibits excellent photocatalytic self-cleaning, UV blocking, and antimicrobial activity. CuGaO2 and CuFeO2 nanoparticle concentrations of 1mM and 2mM were deposited over the cotton fabric …

Electrocatalytic Degradation Of Bisphenol A Using Nickel Sulfide Supported On Graphene Oxide And Cobalt Sulfide Supported On Graphene Oxide Composite Materials, Katherine Ellynn Wright

Theses and Dissertations

The degradation of bisphenol A (BPA) by nickel sulfide supported on graphene oxide (NiS/GO) and cobalt sulfide supported on graphene oxide (CoS/GO) composite materials was investigated. The catalysts were studied to determine the optimal conditions for BPA degradation using electrocatalysis. Electrocatalytic trials were performed using varying parameters, which included electrolyte concentrations of 1.0 g/L, 2.0 g/L, and 4.0 g/L Na2SO4, pHs of 2, 4, and 6, and constant currents of either 0.100 A or 0.200 A. During the reaction samples were taken before the current was applied and 30 minutes and 60 minute intervals to observe the degradation of …

Studies Of Novel And Well-Defined Dinickel Architectures Utilizing An N-Atom Bridge, David Anthony De Los Santos

Theses and Dissertations

There has been a growing interest in organometallic chemistry to utilize late Earth-abundant metals towards challenging molecular functionalization of abundant feedstocks to value-added products. There is precedent of utilizing cooperativity to try and address some of the shortcomings of traditional mononuclear complexes by integrating metal-metal and or metal-ligand cooperativity to facilitate multi-electron transformations. The utility of a redox-noninnocent scaffold allows for the metal centers to be stable over a range of oxidation states, using the ligand to store electrons. Despite recent progress, complexes harnessing cooperative states towards challenging transformations is still an emerging field. Our group has synthesized a multinucleating …

Synthesis Of Nano-Microstructured Barium Titanate (Batio3) Incorporated In Pvdf-Hfp/Peo For Sustainable And Green Energy Generation, Rigobert Ybarra Jr.

Theses and Dissertations

The global reliance on fossil fuels and natural gas, has largely dominated the energy production field, but due to finite resource depletion and escalating greenhouse gas emissions, the immediate exploration of sustainable energy alternatives to mitigate climate change and ensure resource security has been a major concern. There has been extensive research into other more renewable methods of energy production such as wind and hydropower. Of these current energy generation types there are many areas of untapped potential from the mechanical movements generated ambiently not only in the large scale of power generation but also on a smaller scale. The …

Modelling Terrestrial And Potential Extraterrestrial Photopigments Via Density Functional Theory, Dorothea Illner

Theses and Dissertations

In the search for extraterrestrial life, biosignatures play a crucial role in identifying its putative traces. A commonly known and robust biosignature is the Vegetation Red Edge (VRE), which can be described as a sharp increase of reflectance observed from a planet and stems from the light absorption of photopigments in specific regions in the electromagnetic spectrum. For Earth, this VRE is known to occur around 700 nm, however, if the photopigments absorb light in different regions and have different structures the VRE could experience a wavelenght shift.

In this work, Chlorophyll a and a potential photopigment precursor called Phot0 …

Development Of Bifunctional Electrocatalyst For The Electrically Rechargeable Zinc Air Batteries, Thiruvenkatam S

Theses and Dissertations

The spontaneous reaction between zinc and oxygen in an alkaline medium is exploited in non-rechargeable aqueous zinc-air batteries (ZABs) to generate useful electricity. The primary ZAB has a rich history as it was used in tramways, railway signalling and it is being used in hearing aids, pacemakers, etc. The success of primary ZABs led to the development of two types of rechargeable ZAB, namely, mechanically rechargeable ZAB (mrZAB) and electrically rechargeable ZAB (erZAB). In mrZABs, the exhausted anode and electrolyte are replaced periodically. Whereas the chemistry of primary ZAB is reversed using suitable electrocatalysts in erZABs. Electrocatalysts used in erZABs …

The Study Of Biomass Based Polymers And Cyclic Polymers, Yishayah Bension

Theses and Dissertations

Plastics have become an integral part of everyday life, from household care to aerospace applications, polymers are involved in every industry. Most of these polymeric materials are derived from petroleum feedstocks which have deleterious effects on our environment. The production of petrochemicals has led to an increase in greenhouse gases and microplastic pollution which have accelerated climate change. My research focuses on utilizing existing biomasses to improve the plastic economy’s circularity. This work develops new materials from bio-based polymers such as lignin and soybean oil. Raw lignin suffers from inherently weak mechanical properties, poor solubility, processability, and molecular structure ambiguity. …

Advanced Oxidation Of Tert-Butanol With Ultraviolet Light Emitting Diodes And Hydrogen Peroxide, Lauren R. Mainolfi

Theses and Dissertations

Tert-butanol (TBA), a versatile chemical widely used in industrial processes, poses exposure risks through inhalation, ingestion, and skin contact. Environmental contamination, often from industrial activities, emphasizes the importance of robust waste management and monitoring to protect water supplies from potential TBA migration and ensure drinking water safety. This study employed hydrogen peroxide (H2O2): TBA molar ratios of 100, 200, 400, and 500:1 in a Continuous Flow Stirred-Tank Reactor (CSTR) with UV-LED as the TBA degradation mechanism in an Advanced Oxidation Process (AOP). The UV-LEDs and H2O2 were synergistically employed to generate hydroxyl radicals in an advanced oxidation process. Gas chromatography–mass …