Chemistry Commons^™

Diethoxycarbonyl-Bodipys As Heavy-Atom-Free Photosensitizers For Holographic Recording In Cellulose Acetate Photopolymer, Aimee Sheehan, Tatsiana Mikulchyk, Catherine S.P. De Castro, Safakath Karuthedath, Wejdan Althobaiti, Metodej Dvoracek, Sabad-E Gul, Hugh Byrne, FréDéRic Laquai, Izabela Naydenova, Mikhail Filatov

Articles

A series of new heavy-atom-free photosensitizers based on 2,6-diethoxycarbonyl-BODIPY scaffold was designed and applied for holographic recording in a photopolymerizable material. Photoinduced electron transfer between the BODIPY and meso-aryl subunits, followed by the formation of BODIPY triplet excited states via spin-orbit charge transfer intersystem crossing (SOCT-ISC) was studied by steady-state and ultrafast pump-probe transient optical spectroscopy. Highly efficient photosensitization was observed for dyads bearing pyrene and anthracene substituents, which exhibited singlet oxygen generation quantum yields () of up to 94%. Charge transfer and SOCT-ISC were observed in non-polar solvent (toluene) due to the increased electron accepting ability of the diethoxycarbonyl-BODIPY. …

A Simple Microcalorimetry System To Determine The Adsorption Behaviour Of Acids In Large Adhesive Bond Gaps Using Base-Initiated Solution Polymerisation Of Ethyl-2-Cyanoacrylate, Kevin Raheem, John Cassidy, Tony Betts, Bernard Ryan

Articles

This work presents the use of a simple microcalorimetry cyanoacrylate (CA) polymerisation system for investigating aspects of CA adhesive cure through gap and adsorption of adhesive acid stabiliser by a range of metal and glass substrates. It is well established that strong acid induced inhibition periods (IPs) are almost directly proportional to the acid concentration in weak base initiated polymerisations of alkyl CAs in tetrahydrofuran (THF). Ethyl cyanoacrylate (ECA) polymerisation IP measurements were used to determine the adsorption of methanesulfonic acid (MSA) in THF or ECA solutions by a range of metal, glass and polypropylene (PP) lap shears surfaces. The …

Synthesis Of Fluoxetine, Annaliese Franklin, Erica Nelson

Research Awards

No abstract provided.

Investigation Of Factors Affecting Reverse-Phase High Performance Liquid Chromatography, Rida A. Syed

AUCTUS: The Journal of Undergraduate Research and Creative Scholarship

This study focused on the application of reverse-phase high-performance liquid chromatography (RP-HPLC). RP-HPLC is used for the purification of organic molecules, including pharmaceuticals, natural products, and proteins. We developed a modified version of a United States Pharmacopeia (USP) procedure to separate and purify the chemical components found in Excedrin tablets. The goal was to investigate the relationship between retention time (Tr) and the capacity factor (k') of solutes. By varying the composition of the mobile phase and stationary phase, we experimentally determined the capacity factor of acetaminophen (APAP), caffeine, and aspirin. Our results show that the capacity factor (k') of …

Vibrational Spectroscopy For The Detection, Identification, And Differentiation Of Body Fluids And Fingermarks In Forensic Investigations, Samuel Joel Sears

Legacy Theses & Dissertations (2009 - 2024)

This thesis examines the recent literature that has explored the applications of vibrational spectroscopy in forensic science. Specifically, this thesis focuses on how vibrational spectroscopy has improved the detection, identification, and differentiation of body fluid and fingermark evidence in forensic investigations. It is here shown that novel, vibrational spectroscopic techniques have the potential to provide new insights to forensic investigators, and thus revolutionize the field of forensic science. This thesis has been adapted with permission from {Innovative Vibrational Spectroscopy Research for Forensic Application. Alexis Weber, Bailey Hoplight, Rhilynn Ogilvie, Claire Muro, Shelby R. Khandasammy, Luis Pérez-Almodóvar, Samuel Sears, and Igor …

Development Of New Mass Spectrometric Approaches For Biomarker Discovery: Application To Complex Biological Matrices For Tissue Characterization And Disease Diagnosis, Allix Marie Coon

Legacy Theses & Dissertations (2009 - 2024)

In this work, the newly developed technique laser ablation direct analysis in real – time high-resolution imaging mass spectrometry (LADI-MS) and the more established methods direct analysis in real time – high-resolution mass spectrometry (DART-HRMS) and two-dimensional gas chromatography – mass spectrometry (GC×GC-MS), were used to interrogate challenging plant- and human-derived complex matrices that have proven difficult to analyze by conventional methods, in order to extract heretofore inaccessible information that can be applied to the understanding of wood systems biology, ecophysiology, dendrochronology and natural product isolation of biologically relevant compounds (on the plant side), and explore the potential for discovery …

Development Of Ambient Ionization Mass Spectrometry Approaches For The Characterization And Quantification Of Psychoactive Small-Molecule Constituents In Complex Plant Matrices, Megan Isabella Chambers

Legacy Theses & Dissertations (2009 - 2024)

Drug chemistry sections of forensic crime laboratories are tasked with analyzing a variety of unknown materials, a subset of which are derived from plants. In comparison to the analysis of small-molecule drugs, these plant matrices are incredibly complex and present unique challenges. When traditional chromatographic approaches are used to interrogate these materials in forensic investigations, large amounts of time, resources, and funds are directed towards the extensive sample preparation steps required. Exacerbating the issue is that the matrix characteristics often result in instrument downtime to accomplish the maintenance required to address ingredients adhering to columns or clogging syringes, which are …

Dart-Hrms And Chemometric Analysis For Applications In Forensic Entomology, Amy Marie Osborne

Legacy Theses & Dissertations (2009 - 2024)

Forensic entomology, the utilization of insects in the course of legal investigations, is a broad field which encompasses three main branches: medico-legal, stored-product, and urban. This body of research focuses on the first two branches. The first branch, medico-legal forensic entomology, generally applies to death investigations. In death investigations it is imperative to establish the time since death (postmortem interval) and cause of death. Both of these queries can be difficult to assess for remains that are in mid- to late- stages of decay. Carrion insects found on and near the body can assist forensic investigators in this task, as …

Biomimetic Synthesis Of Hitorins A And B And Discovery Of Porous Metallopolymers, Tianran Zhai

Legacy Theses & Dissertations (2009 - 2024)

This work focuses on two research directions: the total synthesis of natural products hitorins A and B and the synthesis of porous metallopolymers/ metallooligomers and study of their properties. Nature has a good understanding and makes good use of cascade reactions to generate complex natural structures. The synthesis of hitorins A and B employed a radical cascade starting from a rare intermolecular alkoxy radical-olefin coupling reaction in our biomimetic synthetic strategy. A radical clock experiment was designed to reveal the mechanism for the key alkoxy radical-olefin coupling cascade. Microporous materials have many applications in diverse areas including gas separation, electronic …

Post-Synthetic Modification Of Metal-Organic Frameworks And Demonstration Of Their Characteristics For Chemistry Education, Audrey Barbara Crom

Legacy Theses & Dissertations (2009 - 2024)

Metal–organic frameworks (MOFs) have risen in popularity in recent decades due to their applications in gas storage, separations, and catalysis. The vast potential of these materials is a result of the inherent characteristics and properties afforded by the composition and combination of ligand and metal clusters used to construct MOFs. In this dissertation, we explore the properties and capabilities of these frameworks from a variety of perspectives. First, we demonstrate the characteristics of MOFs in experiments designed to be suitable for integration in an educational environment. Inorganic chemistry derives many of its concepts from multiple facets of chemistry, which makes …

Functional Comparison Of Full-Length Palladin To Isolated Actin Binding Domain, Sharifah Albraiki, Oluwatosin Ajiboye, Rachel Sargent, Moriah R. Beck

Research, Publications & Creative Work

Palladin is an actin binding protein that is specifically upregulated in metastatic cancer cells but also colocalizes with actin stress fibers in normal cells and is critical for embryonic development as well as wound healing. Of nine isoforms present in humans, only the 90 kDa isoform of palladin, comprising three immunoglobulin (Ig) domains and one proline-rich region, is ubiquitously expressed. Previous work has established that the Ig3 domain of palladin is the minimal binding site for F-actin. In this work, we compare functions of the 90 kDa isoform of palladin to the isolated actin binding domain. To understand the mechanism …

Reducing Disposable Plastic Waste From Protein Quantitative Assays, Justin Buiter

All Capstone Projects

Protein concentration quantification is important for many areas of biology and biochemistry. This quantification happens in large quantities in laboratories and needs to be done accurately and quickly. The Bradford assay is one of the most common ways of accomplishing this task (1). This assay relies on the binding of the protein and the Coomassie Blue G250 dye. The anionic blue form binds to the protein and has a maximum at 595 nm. This allows for accurate quantification by reading how much of the sample absorbs at 595 nm (2).

In 2014, it was estimated that 5.5 million tons of …

Synthetic Studies Of Dragonamide E And Its Potential Treatment Of Leishmaniasis, Sarah E. Glaesemann

Chemistry Theses

Leishmaniasis is a parasitical infection categorized as one of about twenty Neglected Tropical Diseases. Spread by the female sand fly, it can become very severe if left untreated. Symptoms include skin lesions, which may cause scarring, and mucosal membrane infection, which may lead to facial deformity. The most severe form of leishmaniasis can infect organs such as the liver and spleen, possibly leading to death. The current treatments for leishmaniasis are becoming limited due to an increase in drug resistant parasites. Furthermore, the side effects of these treatments can be very problematic.

In the search for new treatments for tropical …

Cryptand-Based Low-Valent F-Block Complexes Toward Stabilization And Separation Of Actinides And Lanthanides, Deshika Nuwangi Kulasekara

Wayne State University Dissertations

ABSTRACTCRYPTAND-BASED LOW-VALENT F-BLOCK COMPLEXES TOWARD STABILIZATION AND SEPARATION OF ACTINIDES AND LANTHANIDES DESHIKA NUWANGI KULASEKARA August 2023 Advisor: Dr. Matthew J. Allen Major: Chemistry (Inorganic) Degree: Doctor of Philosophy This thesis consists of six chapters that include studies of the understanding of ligand environment on the stabilization and separation of low-valent lanthanides and actinides. The studies explain the trends in structural, spectroscopic, and electrochemical properties of lanthanide and actinides with respect to changes in donor atoms, denticity, basicity, and counter ions. This dissertation also discusses a ligand-modified solid–liquid extraction method to separate lanthanide from each other. A brief overview of …

Testing Different Approaches For The Stabilization Of Mdi: Design Of Low-Valent Molybdenum Complexes In Redox-Active Environments And Capture-Release Reactions Using N-Heterocyclic Carbenes, Asanka Indrajith Dissanayake

Wayne State University Dissertations

Methylene diphenyl diisocyanate (4,4’-MDI) is an aromatic diisocyanate, which is widely used as a monomer in the polyurethane industry. One of the main challenges with using 4,4’-MDI is its dimerization into uretdione. The polyurethane industry seeks solutions that could suppress dimerization of 4,4’-MDI and extend its shelf-life. The focus of this dissertation is on the design of chemical solutions to this problem including: (1) reversible coordination of MDI (heteroallene) to low-valent mono- or dimolybdenum complexes in redox-active ligand environment, and (2) reversible coordination of MDI with two equivalents of an appropriate N-heterocyclic carbene.

MDI (isocyanate) is a heteroallene, and heteroallenes …

Hyperpolarized Nitrogen-15 Mri Contrast Agents For Hypoxia Sensing Via Reversible Exchange With Parahydrogen, Mohammad Shah Hafez Kabir

Wayne State University Dissertations

The detection of hypoxia in hypoxic-related diseases can provide crucial information for treatment planning and assessment of therapy response. Although Positron Emission Tomography (PET) was employed as a research tool for imaging of hypoxia detection, it has several limitations. Our motivation is to develop a hyperpolarized (HP) molecular probe for hypoxia sensing. My dissertation presents the utility of Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) to hyperpolarize a wide range of N-heterocyclic compounds, which can be employed as MRI contrast agents for hypoxia sensing and other molecular imaging applications.SABRE-SHEATH is a rapid, simple, cost-effective …

Tie Dye Activity Plans, Admin Stem For Success

STEM for Success Showcase

OVERVIEW:

The STEM for success ambassador program will provide high school students the opportunity to participate in STEM activities that challenge them to learn topics covered in most high school chemistry and physics courses in an environment that cultivates leadership, STEM advocacy, and the 21st century skills of creativity and collaboration. High school students will learn tie-dye science and the chemistry and physics of slime and use their learning experiences to create hands-on activities for Pre-K through 8th grade students. High school students will form teams and venture out into their communities to explore the activities they have created in …

Eps 202-102: Society Techn & Environmnt, Sweeta Chauhan

Chemistry, Environmental and Forensic Science Syllabi

No abstract provided.

Outstanding Advantages, Current Drawbacks, And Significant Recent Developments In Mechanochemistry: A Perspective View, Silvina Pagola

Chemistry & Biochemistry Faculty Publications

Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed …

More On The Demons Of Thermodynamics, Daniel P. Sheehan, Garret Moddel, James W. Lee

Chemistry & Biochemistry Faculty Publications

No abstract provided.

The Effect Of Metalation On Antimicrobial Piscidins Imbedded In Normal And Oxidized Lipid Bilayers, Ana Dreab, Craig A. Bayse

Chemistry & Biochemistry Faculty Publications

Metalation of the N-terminal Amino Terminal Cu(II)- and Ni(II)-binding (ATCUN) motif may enhance the antimicrobial properties of piscidins. Molecular dynamics simulations of free and nickelated piscidins 1 and 3 (P1 and P3) were performed in 3 : 1 POPC/POPG and 2.6 : 1 : 0.4 POPC/POPG/aldo-PC bilayers (POPC, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine: POPG, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol; aldo-PC, 1-palmitoyl-2-(9′-oxo-nonanoyl)-sn-glycero-3-phosphocholine) bilayer models. Nickel(II) binding decreases the conformation dynamics of the ATCUN motif and lowers the charge of the N-terminus to allow it to embed deeper in the bilayer without significantly changing the overall depth due to interactions of the charged half-helix …

Arginine-178 Is An Essential Residue For Itpa Function, Nicholas E. Burgis, Caitlin April, Kandise Vanwormer

Chemistry and Biochemistry Faculty Publications

The inosine triphosphate pyrophosphatase (ITPA) enzyme plays a critical cellular role by removing noncanonical nucleoside triphosphates from nucleotide pools. One of the first pathological ITPA mutants identified is R178C (rs746930990), which causes a fatal infantile encephalopathy, termed developmental and epileptic encephalopathy 35 (DEE 35). The accumulation of noncanonical nucleotides such as inosine triphosphate (ITP), is suspected to affect RNA and/or interfere with normal nucleotide function, leading to development of DEE 35. Molecular dynamics simulations have shown that the very rare R178C mutation does not significantly perturb the overall structure of the protein, but results in a high level of structural …

Structural, Thermal, Optical, And Mechanical Properties Of Composite Films Developed From The Button Mushroom (Agaricus Bisporus)-Sourced High Molecular Weight Chitosan And Potato Starch, Buliyaminu A. Alimi, Monjural Hoque, Shivani Pathania, Jude Wilson, Brendan Duffy, Jesus Maria Frias

Articles

Films were fabricated using the button mushroom (Agaricus bisporus) sourced high molecular weight chitosan with or without potato starch using the casting method. Glycerol was used as the plasticizer. Chitosan content in the film-forming solution (FFS) was varied (0.5, 0.75 and 1.0% w/v of FFS) while potato starch (1.0% of FFS) and glycerol (25% of the total solid content in the solution) contents were not varied. The control sample contained only chitosan (1.0% of the FFS) and glycerol. The effect of increasing the content of chitosan on the rheological properties of FFS and the properties of the films were investigated. …

First Review Of Equilibrium Landscape Of Ingress/Egress Channels And Gating Residues Of The Cytochrome P450 3a4, Edward Ackad Ph.D, Maria Kontoyianni

SIUE Faculty Research, Scholarship, and Creative Activity

The review document and changes made to "Equilibrium Landscape of Ingress/Egress Channels and Gating Residues of the Cytochrome P450 3A4".

Impact Of Sample Conditions On Dna Phosphodiester Backbone Bi/Bii Conformational Equilibrium Dynamics, Autumn C. Pilarski

Graduate Theses/Dissertations

DNA damage, such as single base lesions and mismatches, is highly prevalent within cells. If these DNA damage events are not repaired, they could lead to mutations and thus disease and cancer. Intricate repair mechanisms are in place to fix these damage events, one such being Base Excision Repair (BER) and associated enzyme: Thymine DNA Glycosylase (TDG). The first step of this repair process, recognition of the lesion by TDG, is not well understood. The following thesis presents results to better understand the fundamental biophysical question of how a DNA lesion within a mismatch context is recognized in a million …

Phosphorus Release And Recovery From Simulated Ferric Wastewater Sludge, Aseel Alnimer

Theses and Dissertations (Comprehensive)

Phosphorus (P) is a fundamental element necessary for all life forms and a key component in the fertilizer industry. Meanwhile, the excessive load of P to water bodies due to human activities has the potential to promote eutrophication. Wastewater treatment plants remove P either biologically or chemically and produce P rich sludge which could be a potential renewable source for P. At present, commercial technologies exist for P recovery from biological wastewater sludge. However, P recovery from chemical sludge particularly iron(III)-phosphate (Fe-P) sludge generated in chemical P removal plants that use iron(III) salts remains a challenge.

This study explored, in …

Mechanistic Studies Of Co2 Electrochemical Reduction (Co2er) On Cu And Cuo Nanoparticles With In-Situ Atr-Ftir Spectroscopy, Jason Hsu

Theses and Dissertations (Comprehensive)

Global climate change is a major challenge facing the world in the 21st century. This environmental crisis originated from excess amounts of atmospheric carbon dioxide (CO2) released from burning fossil fuels. One promising remediation method to decrease atmospheric CO2 levels is called carbon dioxide electrochemical reduction (CO2ER). In CO2ER, the CO2 gas undergoes chemical reduction to other hydrocarbon fuels. For CO2ER to take place, an energy source and a catalyst are needed. In this thesis, three aspects of CO2ER were investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy coupled with other surface sensitive characterization tools. First, we studied …

Contrasting Seasonal Cycling Of Arsenic In A Series Of Subarctic Shield Lakes With Different Morphometric Properties, Jeremy Harbinson

Theses and Dissertations (Comprehensive)

The subarctic shield near Yellowknife, Northwest Territories (NWT), is populated with thousands of small lakes (<1.5 km²) and several large lakes. Historic mining activities in the region have left a legacy of environmental impacts and widespread arsenic (As) contamination in both aquatic and terrestrial environments. In particular, several small subarctic lakes near Yellowknife have been previously documented to be contaminated with high levels of As. Subarctic lakes are characterized by seasonal ice-cover that can persist for more than half of the year, yet little is known about the under-ice spatial and seasonal dynamics of As cycling. The objective of …

Design And Synthesis Of Quaternized Hyaluronic Acid-Quercetin-Carrageenan Nanocomplexes For Anticancer Drug Delivery, Ifra Aslam

Chulalongkorn University Theses and Dissertations (Chula ETD)

The objective of this research is to synthesize a polyelectrolyte nano-complex for anticancer drug delivery, utilizing natural biopolymers with enhanced therapeutic capabilities, biodegradability, and low toxicity. Traditional anticancer drugs are often hydrophobic and pose significant challenges in delivery, as well as causing toxicity to normal cells. In this study, Plai extract, known for its anticancer properties, was employed into a novel polyelectrolyte complex carrier composed of quaternized hyaluronic acid-quercetin (Quat-HA-QT) with carrageenan. The design involved: (i) utilizing hyaluronic acid (HA) for its CD-44 receptor affinity on tumor cells, (ii) modifying HA with Quat-188 to impart a positive charge and incorporating …

Virtual Simulation Platform To Support Learning In Column Selection For Gas Chromatography, Lianrong Zhang

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this research, a virtual simulation platform was developed to support lecture-based teaching for gas chromatography (GC) coupled with a flame ionization (FID) detector. This platform utilizes a computerized three-dimensional (3D) model created using Blender, Unity, Visual Studio, and starter assets programs. It mimics laboratory and experimental learning to optimize GC conditions, including column types, column length, column diameter, gas flow rate, and sample injection for the separation of kerosene, derivatized milk, and perfume from sources such as aircraft, plants, and perfume samples. A spreadsheet-based simulation was used to simulate chromatograms of defined chemical compositions under various conditions. The retention …