Chemistry Commons^™

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 …

Toxicity Of Waterpipe Tobacco Smoking: The Role Of Flavors, Sweeteners, Humectants, And Charcoal, Nada O F Kassem, Robert M. Strongin, Andrea M. Stroup, Marielle C. Brinkman, Ahmad El-Hellani, Hanno C. Erythropel, Arash Etemadi, Maciej L. Goniewicz, Eleanore G. Hansen, Noura O. Kassem, Multiple Additional Authors

Chemistry Faculty Publications and Presentations

Waterpipe tobacco (WPT) smoking is a public health concern, particularly among youth and young adults. The global spread of WPT use has surged since the introduction of pre-packaged flavored and sweetened WPT, which is widely marketed as a safer tobacco alternative. Besides flavorants and sugars, WPT additives include humectants, which enhance the moisture and sweetness of WPT, act as solvents for flavors, and impart smoothness to the smoke, thus increasing appeal to users. In the United States (U.S.), unlike cigarette tobacco flavoring (with the exception of menthol), there is no FDA product standard or policy in place prohibiting sales of …

Policy Overview (June, 2024)

Bulletin of Chinese Academy of Sciences (Chinese Version)

No abstract provided.

News Flash

Bulletin of Chinese Academy of Sciences (Chinese Version)

No abstract provided.

Activity: Students Find Conceptual Errors In Ai Output, Janie Brennan

Generative AI Teaching Activities

Instructor asks ChatGPT questions related to a key concept to find one where ChatGPT has conceptual errors. Ask students to find the errors and explain them.

Synergistic Antioxidant And Antibacterial Effects Of A Zn-Ascorbate Metal-Organic Framework Loaded With Marjoram Essential Oil, Rana R. Haikal, Noha El Salakawy, Alaa Ibrahim, Shaimaa L. Ali, Wael Mamdouh

Faculty Journal Articles

Antimicrobial resistance (AMR) has become an immense threat to public health leading to an urgent need for development of new technologies to tackle such a challenge. Plant-based drugs, specifically essential oils (EOs) and plant extracts, have shown significant potential as effective green antimicrobial agents. However, they suffer from high volatility and low thermal stability resulting in their inefficient utilization in commercial settings. Among the various nanoencapsulation technologies reported, metal-organic frameworks (MOFs) have been recently investigated as potential nanocarriers of EOs in attempt to enhance their stability. Herein, we report the utilization of Zn-ascorbate MOF for the encapsulation of marjoram essential …

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 …

Chemical And Morphological Characterization Of Airborne Particulate Matter At The Jackpile-Paguate Mine, Pueblo Of Laguna, New Mexico: Implications For Potential Metals Exposure, Andreanna C. Roros

Earth and Planetary Sciences ETDs

The inhalation of windblown particulate matter (PM) derived from abandoned uranium mines (AUMs) is a potential environmental health risk to Native American communities that live in proximity to these sites. However, the aeolian transport of metal-bearing PM from AUMs, as a potential exposure pathway, has not been investigated in any detail. In this study, we sampled airborne particulate matter within the Jackpile Mine located on the lands of the Pueblo of Laguna, New Mexico using passive sampling methods to understand the characteristics of dust within the mine site. The objective was to determine the elemental concentrations, mineralogy, and morphology of …

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 …

Iron Oxide Nanozymes Enhanced By Ascorbic Acid For Macrophage-Based Cancer Therapy, Zhongchao Yi, Xiaoyue Yang, Ying Liang, Sheng Tong

Markey Cancer Center Faculty Publications

In recent years, using pharmacological ascorbic acid has emerged as a promising therapeutic approach in cancer treatment, owing to its capacity to induce extracellular hydrogen peroxide (H2O 2) production in solid tumors. The H2 O 2 is then converted into cytotoxic hydroxyl free radicals (HO•) by redox-active Fe2+ inside cells. However, the high dosage of ascorbic acid required for efficacy is hampered by adverse effects such as kidney stone formation. In a recent study, we demonstrated the efficient catalytic conver- sion of H2 O2 to HO• by wüstite (Fe 1−xO) nanoparticles (WNPs) through a heterogenous Fenton reaction. Here, we explore …

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, …

Synthesis And Analysis Of Borazine Polymers, Kayla M. Besel

2024 Symposium

Plastics and polymers are incredibly useful and ubiquitous in our daily lives but they are incredibly persistent in the environment, killing more than 1.1 million seabirds and animals each year and the global production of plastic has doubled since 1950.¹ A potential path to eliminate this problem is to create polymers that biodegrade or breakdown over time or in certain conditions. Three distinct degradable polymers were synthesized. The synthesis, characterization, and kinetics monitored by UV/Vis over a range of pH’s will be discussed.

1. Derraik, J. G. B. “The pollution of the marine environment by plastic debris: a review” …

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 …

Kinetics Of Selenate Reduction Mediated By Underpotentially Deposited Cu On Polycrystalline Au Electrodes In Aqueous Perchloric Acid, Jonathan Strobl, Saurabh Pathak, Daniel Scherson

Faculty Scholarship

The reduction of selenate, SeO²₄⁻(aq),in 0.1 M HClO₄ solutions, induced by underpotential deposition, UPD, of Cu on polycrystalline Au electrodes was investigated using the rotating ring-disk electrode, RRDE, technique. Design and implementation of electrode potential-rotation rate protocols made it possible to determine the rates of SeO²₄⁻(aq)reduction as a function of Cu coverage, θCu, as determined by the Bruckenstein method (Swathirajan et al. J. Phys. Chem. 1982, 86, 2480–2485). In agreement with the results reported recently for Au(111) film electrodes (Strobl et al. Electrochimica Acta 2024, 493, 144,298), the reaction was found to proceed only for θCu above a critical value, …

Cutting-Edge Developments In Zinc Oxide Nanoparticles: Synthesis And Applications For Enhanced Antimicrobial And Uv Protection In Healthcare Solutions, Egwonor Loveth Irede, Raymond Femi Awoyemi, Babatunde Owolabi, Omowunmi Rebecca Aworinde, Rofiat Odunayo Kajola, Ajibola Hazeez, Ayuba Adawale Raji, Latifat Oluwatobi Ganiyu, Chimezie O. Onukwuli, Asishana Paul Onivefu, Ikhazuagbe Hilary Ifijen

Michigan Tech Publications

This paper presents a comprehensive review of recent advancements in utilizing zinc oxide nanoparticles (ZnO NPs) to enhance antimicrobial and UV protective properties in healthcare solutions. It delves into the synthesis techniques of ZnO NPs and elucidates their antimicrobial efficacy, exploring the underlying mechanisms governing their action against a spectrum of pathogens. Factors impacting the antimicrobial performance of ZnO NPs, including size, surface characteristics, and environmental variables, are extensively analyzed. Moreover, recent studies showcasing the effectiveness of ZnO NPs against diverse pathogens are critically examined, underscoring their potential utility in combatting microbial infections. The study further investigates the UV protective …

Tribocorrosion And Metal Release From Austenitic Stainless Steels 304 And 201 In Simulated Cassava Food Contact, Robert Addai, Temitope E. Olowoyo, Thalia E. Standish, Jeffrey Daniel Henderson, Ubong Eduok, Yolanda Hedberg

Chemistry Publications

Cassava is the third most significant calorie source in the tropics. Its processing has changed from traditional methods to stainless steel processing machines. This study investigated the influence of cassava on metal release from two common stainless steels, ASTM 304 and 201, with and without friction, and on tribocorrosion (multianalytically) of 304. Cassava was relatively corrosive and hindered repassivation of the surface oxide of stainless steel, but it also acted as a lubricant against mechanical friction. The combined action of friction and cassava caused a significant increase in iron, chromium, nickel, and manganese release from the stainless steels (30–35- fold …

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: …

Synthesis And Characterization Of Cobalt-Based Complexes And Metal-Organic Frameworks For Hydrogen Evolution Catalysis Under Acidic Conditions, Elizabeth A. Tonsel-White

Chemistry & Biochemistry Theses & Dissertations

The synthesis of two cobalt(II) complexes: the novel complex [Co(phen)₃]₂[Co(pytc)₂]•16.25H₂O 1 and the previously reported [Co(bpy)₃](OH)₂•7H₂O 2, along with a cobalt(II/III)-containing MOF, Co-PPF2, previously reported as well, was achieved. These complexes were characterized by elemental analysis, X-ray crystallography, microscopy, conductivity measurements, TGA, SEM, CV , and UV-visible , and FTIR spectroscopies. From the CV scan rates, diffusion coefficients for complexes 1 and 2 were determined to be 1.0 × 10⁻⁶ cm² s⁻¹ and 4.8 × 10⁻⁷ cm² s⁻¹. Electrocatalytic studies with complexes 1 and 2 revealed insights into the mechanistic aspects of …

The Chemistry Of Heavy Elements: Probing Relativistic Chemical Bonding, Barbara Maria Teixeira Costa Peluzo

Chemistry Theses and Dissertations

The bottommost part of the periodic table has a unique chemistry, where the high velocities of the inner-shell electrons prevent their description by the usual Schrödinger equation. The resulting so-called relativistic effects have numerous chemical implications, on both macro and microscale, ranging from physical properties to reactivity. However, experimental probes on these intriguing atoms are limited by their natural availability and, more importantly, the danger associated with their radioactivity. Quantum chemical calculations, on the other hand, face the challenge of far more complex algebra, which demands substantial computational resources. Relativistic Hamiltonians, which act over all electrons in the system, are …

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 …