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Chemical Recycling Of Bio-Based Polyurethane Foams: Evaluating Bio-Based Glycols In Comparison To Petroleum-Based Glycols, Anirudh Thorbole Mr.

Electronic Theses & Dissertations

The paradigm shift towards bio-based polyurethane foams (bio-PUF) has significantly increased post-consumer waste. To address this issue, this research represents a novel approach to enhance sustainable development in the recycling industry by replacing traditional petroleum-based glycols with sustainable bio-based alternatives. This study explores the glycolysis of bio-PUF using bio-based SG-522 glycol and polyethylene glycol (PEG) for comparison. The findings from this research as outlined, reveal no significant differences in depolymerization time between the two glycols, achieving proper depolymerization and high recovery yields of over 95% after solvent purification. Comprehensive FT-IR and NMR analyses confirmed the successful degradation of bio-PUF and …

Excited State Processes In Radical Elaborated Platinum Donor-Acceptor Complexes, Sangita Paudel

Chemistry and Chemical Biology ETDs

Organo-transition metal complexes are being widely studied to understand their photophysical properties for their wide range of applications as efficient emitters in organic light emitting diodes (OLEDs), light emitting electrochemical cells (LEECs), etc. Cyclometalated organo-transition metal complexes such as cyclometalated square planar platinum(II) complexes are becoming suitable candidates for such applications because of their highly efficient luminescence. Understanding the excited properties of such complexes is useful in designing highly efficient and color tunable phosphors with desired excited state lifetimes. We aim to explore the influence of radical substituents on electronic structure, luminescence quantum efficiencies, and excited state lifetimes by synthesizing …

Cross-Correlation Increases Sampling In Diffusion-Based Super-Resolution Optical Fluctuation Imaging, Jeanpun Antarasen, Benjamin Wellnitz, Stephanie N. Kramer, Surajit Chatterjee, Lydia Kisley

Faculty Scholarship

Correlation signal processing of optical three-dimensional (x, y, t) data can produce super-resolution images. The second-order cross-correlation function XC2 has been documented to produce super-resolution imaging with static and blinking emitters but not for diffusing emitters. Here, we both analytically and numerically demonstrate cross-correlation analysis for diffusing particles. We then expand our fluorescence correlation spectroscopy super-resolution optical fluctuation imaging (fcsSOFI) analysis to use cross-correlation as a postprocessing computational technique to extract both dynamic and structural information on particle diffusion in nanoscale structures simultaneously. Cross-correlation maintains the same super-resolution as auto-correlation while also increasing the sampling rates to reduce aliasing for …

Impact Of Aureobasidium Species Strain Improvement On The Production Of The Polysaccharide Pullulan, Thomas P. West

Faculty Publications

This review explores the production of the fungal polysaccharide pullulan by mutants and natural isolates of Aureobasidium species using strain improvement. Pullulan is a neutral polysaccharide gum whose structure is a maltotriose-containing glucan. This polysaccharide gum has applications in the fields of food, pharmaceuticals, biomedical and wastewater treatment. The strain improvement of Aureobasidium species has focused on the pullulan production process, including the isolation of strains exhibiting reduced pigmentation, polysaccharide overproduction, the production of pullulan with variable molecular weight, and increased osmotolerant strains promoting pullulan production at high carbon source concentrations and pullulan production on hemicellulosic substrates. The majority of …

Freedom As The Physical Notion. Mechanics Of A Material Point, Michael Vigdorowitsch

Karbala International Journal of Modern Science

This is a novel conceptual attempt to introduce freedom as a consistent physical notion. The present consideration is limited to mechanics of a material point. Adapted to physical representation, freedom is tested throughout the paper to conform to its general perception. It is first tried on such physical notions (but not restricted to) as potency of a set, Lagrangian, action, degrees of freedom. Defined as angular and essentially nonlinear variable, it appears to be dual as that the domain affords and that the material point possesses within the domain, not necessarily equal to one another. Freedom has to degrade if …

The Potential Influence Of Immune Modulatory Molecules (Tgf-Βiii And Ctla-4) In Pathogenicity Of Pcos, Mustafa Riyadh Abdullah, Hazima Mossa Alabassi

Karbala International Journal of Modern Science

Polycystic ovary syndrome (PCOS) is characterised by chronic anovulation, hyperandrogenism, polycystic ovaries, and immunological dysregulation. Immune homeostasis and inflammation management require immune functions. T-regulatory cells (Tregs) regulate PCOS's immune system, inflammation, insulin resistance, ovarian function, and homeostasis. Transforming growth factor βIII (TGF-βIII) and Cytotoxic-T-lymphocyte-associated-protein-4 (CTLA-4) receptors on the surfaces of Treg cells are important for controlling the immune system. The study included 68 PCOS patients and 22 non-PCOS women controls aged 20–45. The waist-hip ratio (WHR) determines obesity. We evaluated serum levels and gene expression of TGF-βIII and CTLA-4 via ELISA and real-time PCR. Women with PCOS had significantly higher …

Enhanced Optoelectronics Performance Of Hybrid Self Power Photodetectors Go: Tio2- Ad / N-Si Heterojunctions, Mohammed J. Alsultani, Maysoon F. Alias

Karbala International Journal of Modern Science

A GO:TiO₂/n-Si heterostructure has been submerged in an anthocyanin dye solution that extracted from the red cabbage plant creates a high responsivity, self-powered UV, and visible photodetectors fabricated by the spray pyrolysis technique. The GO concentrations are varied, whereas TiO₂ is fixed. Thin films' structure, shape, and optical characteristics were examined using X-ray diffraction, field emission scanning electron microscopy, and UV-Vis spectrophotometers respectively. Island-like polycrystalline film powders with grain boundaries and granular shapes are created. Two direct energy gaps between 3.33-3.02 and 2.39-2.04 eV exist in all films. J-V characteristics were examined. The saturation current density (J …

Novel Approaches To The Activation Of Chalcogenoglycosides For O-Glycosylation, Tiffany Duong

LSU Doctoral Dissertations

Carbohydrates are integral to various biological processes such as cell signaling, function and regulation. Carbohydrates also play critical roles in various disease and metastatic pathways. This has garnered considerable attention to the field of glycoscience, however, the study of carbohydrate-containing compounds remains a challenge due to the difficulty in obtaining pure samples from natural sources. As a result, the biological evaluation of carbohydrates relies on synthetic chemistry to produce pure compounds in significant quantities. However, the synthesis of carbohydrates present their own challenges owing to the complexity in controlling stereochemistry and regiochemistry. The most significant of these challenges is controlling …

Synthesis And Computational Studies Of Α- And Δ-Substituted Macrocyclic Europium And Ytterbium Complexes, Delainey Amara Winder

Dissertations and Theses

The uses of macrocyclic lanthanide complexes are vast, with many targeted MRI contrast agents at the forefront of the field. Many of these are ParaCEST agents, which require exchangeable protons accessible on the macrocycle and the slow exchange of coordinated water molecules. The substitution at both the α- and δ-carbon on the amide pendant arm of these macrocyclic lanthanide complexes can lock bulky groups on the δ-carbon to a pseudo-axial position. When the α- and δ-carbons have the same chirality, the bulky group will be pseudo-equatorial, and when the chirality is opposed, the bulky group will be pseudo-axial. By performing …

Advances In Stereoselective Glycosylation: Electron-Withdrawing Groups, Benzyne-Mediated Stereoinversion, And Visible-Light Photochemistry For 1,2-Cis O-Glycosylation, Erik Giovanni Alvarez Valenzuela

LSU Doctoral Dissertations

The symbiotic relationship between humans and their microbiota is essential for health, with imbalances in the complex microbiota ecosystem linked to a variety of disorders ranging from neurodegenerative to gastrointestinal diseases. Bacteria within the human microbiota, comprising over 1000 known species, are densely and diversely coated with oligosaccharides crucial for functions like cell recognition, communication, signaling, adhesion, proliferation, and pathogenic inhibition. However, studying the structure-activity relationships of these sugars which are also secreted by bacteria is challenging due to difficulties in obtaining homogenous samples from natural sources.

Chemical synthesis offers a solution by enabling the production of well-defined oligosaccharides in …

Investigation Of Solvation Structures And Dynamics Of Li-Ion Battery Electrolytes And Amides In Water: An Infrared Spectroscopy, Electrochemical And Computational Study, Ernest O. Nachaki

LSU Doctoral Dissertations

The investigation of solvation structures and dynamics in lithium-ion battery electrolytes and amides in water has significant implications for both fundamental science and practical applications. Understanding the solvation dynamics of lithium electrolytes can lead to the development of safer and more efficient LIBs. The study of hydrogen bond dynamics of N-alkyl substituted amides has important implications for the development of thermos-responsive polymers used in biomedical applications. By understanding how N-alkyl substitutions affect the hydration structure and dynamics of amides, this research can inform the design of polymers with tailored properties for drug delivery, tissue engineering, and other medical applications. This …

Theoretical And Spectroscopic Insights Into Molybdenum- And Tungsten-Sulfur Bonding, Jesse Lepluart

Chemistry and Chemical Biology ETDs

Molybdenum and tungsten chemistry in biology is dominated by bonding interactions with sulfur and the other chalcogens. The highly-conserved structures of these enzymes’ active sites suggest an early evolution in the history of life, with molybdenum and/or tungsten enzymes likely expressed by the last universal common ancestor. Despite their active site similarities, molybdenum and tungsten enzymes catalyze a diverse array of reactions via equally diverse mechanisms. A deep understanding of the electronic structures of these enzyme active sites and their catalytic intermediates is key to understanding this remarkable chemistry.

The work presented here aims to deepen the understanding of molybdenum …

Kinetic Characterization And Identification Of Key Active Site Residues Of The L-Aspartate N-Hydroxylase, Cree, Sydney B. Johnson, Hannah Valentino, Pablo Sobrado

Chemistry Faculty Research & Creative Works

CreE is a flavin-dependent monooxygenase (FMO) that catalyzes three sequential nitrogen oxidation reactions of L-aspartate to produce nitrosuccinate, contributing to the biosynthesis of the antimicrobial and antiproliferative nautral product, cremeomycin. This compound contains a highly reactive diazo functional group for which the reaction of CreE is essential to its formation. Nitro and diazo functional groups can serve as potent electrophiles, important in some challenging nucleophilic addition reactions. Formation of these reactive groups positions CreE as a promising candidate for biomedical and synthetic applications. Here, we present the catalytic mechanism of CreE and the identification of active site residues critical to …

Kinetic Characterization And Identification Of Key Active Site Residues Of The L-Aspartate N-Hydroxylase, Cree, Sydney B. Johnson, Hannah Valentino, Pablo Sobrado

Chemistry Faculty Research & Creative Works

CreE is a flavin-dependent monooxygenase (FMO) that catalyzes three sequential nitrogen oxidation reactions of L-aspartate to produce nitrosuccinate, contributing to the biosynthesis of the antimicrobial and antiproliferative natural product, cremeomycin. This compound contains a highly reactive diazo functional group for which the reaction of CreE is essential to its formation. Nitro and diazo functional groups can serve as potent electrophiles, important in some challenging nucleophilic addition reactions. Formation of these reactive groups positions CreE as a promising candidate for biomedical and synthetic applications. Here, we present the catalytic mechanism of CreE and the identification of active site residues critical to …

Development Of Peptidomimetics Based On Γ-Aapeptide Molecular Scaffolds To Modulate Amyloid Peptide Aggregation, Heng Liu

USF Tampa Graduate Theses and Dissertations

Many proteins contain fragments that become structured upon binding to specific targets or through self-association. Notable examples of such disorder-to-order transitions include amyloidogenic proteins like amyloid-β peptide (Aβ) and tau peptide in Alzheimer's disease, α-Synuclein in Parkinson's disease, and hIAPP in type 2 diabetes, and so on. These regions can aggregate into amyloid fibrils through β -sheet stacking, contributing to amyloidosis and related diseases. Although direct link between amyloid formation and neurodegenerative disease development is not fully understood, developing effective inhibitors of these amyloid peptides remains promising both for fundamental research and therapeutical advance.

We have developed a new class …

Functional And Structural Analysis Of The Neimann-Pick Disease Type C Pathway To Include Caveolin-1, Anthony Michael Seat

Chemistry and Chemical Biology ETDs

Human disease is often thought of as an all or nothing prospect, either one has the disease or one does not. This does not bear out in clinical or personal experiences, instead demonstrating that disease occurs within a spectrum ranging from presumed unaffected to demonstrably and detrimentally affected.Neimann-Pick disease is one example of this spectrum look into diseased states, with multiple named versions of a phenotypically similar disease. We focus on Neimann-Picktype C (NPC), which is the result of a disruption in the efflux of cholesterol and sphingolipids from the endocytic pathway. NPC demonstrates this concept of a spectrum of …

Regioselective Hydroamination Of Unactivated Olefins With Diazirine And Total Synthesis Of Nostodione A And Scytonemin, Qingyu Xing

USF Tampa Graduate Theses and Dissertations

As an atom-economic way of carbon-nitrogen bond formation, hydroaminations are great tool for make amines, hydrazines, and other nitrogen-containing heterocycles. Specifically, radical hydroamination is a useful approach for functionalization of unactivated olefins, especially in sterically hindered environments. Diversification remains a challenge for radical hydroaminated products, since the nitrogen sources are carefully designed. In the first chapter of this dissertation, we report a highly diversifiable radical hydroamination reaction with diazirine as a nitrogen source and its potential applications in synthesis of several pharmaceutical interested compounds. Cobalt catalyzed regioselective hydroamination with diazirine shows wide function group tolerance, like phenyl thioether, ketones, esters, …

Detection And Quantification Of Acetaminophen In Aquatic Samples From Cádiz, Spain, Hannah R. Desmarais, Michelle N. Mikos

DePaul Discoveries

Pharmaceutical contaminants in water are becoming increasingly prevalent. This could have potentially harmful effects on human health and aquatic environments, even at low concentrations. Acetaminophen, the active ingredient of Tylenol ®, was the target compound for this study, and the aim was to determine is presence and concentration in various aquatic samples in and around the city of Cádiz, Spain. It was predicted that acetaminophen would be detected in low concentrations in river water, drain outflow, University of Cádiz saltwater flow, and lagoon water, but undetectable in the University of Cádiz sink water and fountain water. The presence and concentration …

Revealing Structural Evolution Of Nickel Phosphide-Iron Oxide Core–Shell Nanocatalysts In Alkaline Medium For The Oxygen Evolution Reaction, Ryan H. Manso, Jiyun Hong, Wei Wang, Prashant Acharya, Adam S. Hoffman, Xiao Tong, Feng Wang, Lauren F. Greenlee, Yimei Zhu, Simon R. Bare, Jingyi Chen

Chemistry & Biochemistry Faculty Publications and Presentations

Metal phosphide-containing materials have emerged as a potential candidate of nonprecious metal-based catalysts for alkaline oxygen evolution reaction (OER). While it is known that metal phosphide undergoes structural evolution, considerable debate persists regarding the effects of dynamics on the surface activation and morphological stability of the catalysts. In this study, we synthesize NiP_x-FeO_x core–shell nanocatalysts with an amorphous NiP_x core designed for enhanced OER activity. Using ex situ X-ray absorption spectroscopy, we elucidate the local structural changes as a function of the cyclic voltammetry cycles. Our studies suggest that the presence of corner-sharing octahedra in the …

Fundamental Limits In Measuring The Anisotropic Rotational Diffusion Of Single Molecules, Weiyan Zhou, Tingting Wu, Matthew D. Lew

Electrical & Systems Engineering Publications and Presentations

Many biophysical techniques, such as single-molecule fluorescence correlation spectroscopy, Förster resonance energy transfer, and fluorescence anisotropy, measure the translation and rotation of biomolecules to quantify molecular processes at the nanoscale. These methods often simplify data analysis by assuming isotropic rotational diffusion, e.g., that molecules wobble within a circular cone. This simplification ignores the anisotropy present in many biological contexts that may cause molecules to exhibit different degrees of diffusion in different directions. Here, we loosen this assumption and establish a theoretical framework for describing and measuring anisotropic rotational diffusion using fluorescence imaging. We show that anisotropic wobble is directly quantified …

Removing Methane Via Atmospheric Oxidation Enhancement: The Legal Framework, Romany M. Webb, Martin Lockman, Korey Silverman-Roati

Sabin Center for Climate Change Law

To achieve the Paris Agreement’s goal of limiting the increase in global average temperatures to “well below 2 degrees Celsius,” and ideally 1.5 degrees Celsius, above pre-industrial levels, global greenhouse gas (“GHG”) emissions must reach net zero in the second half of the century. The global community is not currently on track to achieve net zero emissions. In fact, with the exception of a slight dip during the Covid-19 pandemic, emissions have risen steadily in recent years. This, together with the increasingly visible impacts of climate change, has prompted growing interest in the possibility of removing GHGs directly from the …

Use Of Cobalt(Iii) And Copper(Ii) Complexes With Thiosemicarbazone Ligands And Berberine Chloride As Anti-Cancer Agents Against Triple Negative Breast Cancer, Duaa Rashad Alajroush

Chemistry & Biochemistry Theses & Dissertations

It is a worrying fact that chemotherapeutic options for treating triple negative breast cancer are limited in nature, including the use of inorganic pharmaceuticals such as cisplatin and its analogues. It has been reported that cisplatin has undesirable side effects when used as a chemotherapeutic drug. As such, there is a need to use non-platinum-containing complexes as chemotherapeutic agents. Based on that issue, it has been reported by our research group and others that cobalt- and copper-containing complexes have shown great potential in anti-cancer properties when compared to cisplatin. In this research project, the cytotoxic effects of the following complexes: …

Exploring The Effects Of An Alfalfa Leaf-Derived Adsorbent On Microbial Community, Ileal Morphology, Barrier Function, And Immunity In Turkey Poults During Chronic Aflatoxin B1 Exposure, Maria De Jesus Nava-Ramirez, Jing Liu, Juan Omar Hernandez-Ramirez, Xochitl Hernandez-Velasco, Juan D. Latorre, Alma Vazquez-Duran, Guolong Zhang, Roberto Señas-Cuesta, Sergio Gomez-Rosales, Andressa Stein, Billy M. Hargis, Guillermo Tellez-Isaias, Abraham Mendez-Albores, Jesus A. Maguey-Gonzalez

Poultry Science Faculty Publications and Presentations

This article follows-up on our recently published work, which evaluated the impact of the addition of an alfalfa leaf-derived adsorbent in the aflatoxin B₁ (AFB₁)-contaminated diet in regard to the production parameters, blood cell count, serum biochemistry, liver enzymes, and liver histology of turkey poults. This paper presents complementary results on microbial community, ileal morphology, barrier function, and immunity. For this purpose, 350 1-day-old female turkey poults were randomly distributed into five groups: (1) Control, AFB₁-free diet; (2) AF, AFB₁-contaminated diet at 250 ng/g; (3) alfalfa, AFB₁-free diet + 0.5% ( …

Poly(Thioether) Thermosets With Gated Photodegradation, Surabhi Jha

Dissertations

Photodegradable polymer networks are attractive due to the precise spatiotemporal control and large-area applicability of light. Chemical linkages that enable these polymer networks to be photo-responsive, also hinder their applicability in ambient light. Photostable and photodegradable networks have recently been reported to overcome this challenge by combining other stimuli with light for degradation. We report the design of a network that responds to a simultaneous, dual stimulus for photodegradation. We design poly(thioether acetal) networks with benzylidene acetal moieties that are known to undergo β-scission in the presence of free thiols. By blocking these free thiols with a thermally labile protecting …

Establishment Of Protocols To Measure Near-Ir(Nir) Surface-Enhanced Raman Scattering (Sers) Signals Of Nir Dye, Justin B. Ramsey

Forensic Science Master's Projects

Biomedical imaging techniques are crucial for early disease diagnostics, particularly for life-threatening conditions. However, traditional methods have inherent limitations, such as restricted spatial resolution and potential risks associated with repeated exposure to ionizing radiation. Near-infrared (NIR) surface-enhanced Raman spectroscopy (SERS) presents a promising alternative due to its minimal risks and potential for high-resolution biomedical imaging. A key challenge in NIR-SERS biomedical imaging is the development of biocompatible, nontoxic SERS substrates that can be safely introduced into the human body, targeting specific cells and tissues effectively.

NIR-SERS substrates typically consist of gold nanoparticles (AuNPs) modified with biorecognition elements and reporter molecules, …

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 …

Response To Replication Stress And Maintenance Of Genome Stability By Wrn, The Werner Syndrome Protein, David K. Orren, Amrita Machwe

Markey Cancer Center Faculty Publications

Werner syndrome (WS) is an autosomal recessive disease caused by loss of function of WRN. WS is a segmental progeroid disease and shows early onset or increased frequency of many characteristics of normal aging. WRN possesses helicase, annealing, strand exchange, and exonuclease activities and acts on a variety of DNA substrates, even complex replication and re- combination intermediates. Here, we review the genetics, biochemistry, and probably physiological functions of the WRN protein. Although its precise role is unclear, evidence suggests WRN plays a role in pathways that respond to replication stress and maintain genome stability particularly in telomeric regions.

Carbon-Based Nanocomposite Membranes For Membrane Distillation: Progress, Problems And Future Prospects, Chhabilal Regmi, Yuwaraj K. Kshetri, S. Ranil Wickramasinghe

Chemical Engineering Faculty Publications and Presentations

The development of an ideal membrane for membrane distillation (MD) is of the utmost importance. Enhancing the efficiency of MD by adding nanoparticles to or onto a membrane’s surface has drawn considerable attention from the scientific community. It is crucial to thoroughly examine state-of-the-art nanomaterials-enabled MD membranes with desirable properties, as they greatly enhance the efficiency and reliability of the MD process. This, in turn, opens up opportunities for achieving a sustainable water–energy–environment nexus. By introducing carbon-based nanomaterials into the membrane’s structure, the membrane gains excellent separation abilities, resistance to various feed waters, and a longer lifespan. Additionally, the use …