Chemistry Commons^™

Multivalency Regulates Activity In An Intrinsically Disordered Transcription Factor, Sarah Clark, Janette B. Myers, Ashleigh King, Radovan Fiala, Jiri Novacek, Grant Pearce, Steve L. Reichow, Elisar J. Barbar

Chemistry Faculty Publications and Presentations

The transcription factor ASCIZ (ATMIN, ZNF822) has an unusually high number of recognition motifs for the product of its main target gene, the hub protein LC8 (DYNLL1). Using a combination of biophysical methods, structural analysis by NMR and electron microscopy, and cellular transcription assays, we developed a model that proposes a concerted role of intrinsic disorder and multiple LC8 binding events in regulating LC8 transcription. We demonstrate that the long intrinsically disordered C-terminal domain of ASCIZ binds LC8 to form a dynamic ensemble of complexes with a gradient of transcriptional activity that is inversely proportional to LC8 occupancy. The preference …

Imide Arylation With Aryl(Tmp)Iodonium Tosylates, Souradeep Basu, Alexander H. Sandtorv, David R. Stuart

Chemistry Faculty Publications and Presentations

Herein, we describe the synthesis of N-aryl phthalimides by metal-free coupling of potassium phthalimide with unsymmetrical aryl(TMP)iodonium tosylate salts. The aryl transfer from the iodonium moiety occurs under electronic control with the electronrich trimethoxyphenyl group acting as a competent dummy ligand. The yields of N-aryl phthalimides are moderate to high and the coupling reaction is compatible with electron-deficient and sterically encumbered aryl groups.

Investigations Into Ring-Opening Polymerization Of Functionalized Ε-Caprolactones, Danielle N. Coderre, Matthew K. Kiesewetter

Senior Honors Projects

Polymers are defined as large molecules constructed from small, repeating units (monomers) which make up everyday items, such as: plastic bags and bottles, waterproof coatings, pipes, etc. H-bonding urea (U) or thiourea (TU) catalysts paired with base cocatalysts used for organocatalytic ring-opening polymerization (ROP) of cyclic esters have been shown to exhibit fast rates of polymerization and result in polymers with controlled molecular weights (Mn) and low polydispersity indexes (PDI). Additionally, organocatalytic ring-opening polymerization (ROP) techniques have been shown to be tolerant of the incorporation of functional groups into the monomer feed, which is vital for the catalytic synthesis of …

Detection And Assay Of Isoniazid Utilizing Isocratic High-Performance Liquid Chromatography, Cassandra Nguyen

Theses/Capstones/Creative Projects

To demonstrate an analysis for isoniazid from aqueous mixtures and solid tablets, utilizing isocratic conditions, with high performance liquid chromatography (HPLC) and UV detection. Isoniazid in solid and liquid samples is assayed utilizing HPLC. Isoniazid is a tuberculostat, that is assayed by high performance liquid chromatography that utilizes a reversed-phase C-18 column. The eluent solvent is 5.3% ethanol, 93.7% water, and 1% acetic acid. Aqueous samples are prepared in distilled water as the solvent. The ultraviolet-visible detection of isoniazid is accomplished at 265 nm, which is the wavelength having the highest sensitivity for isoniazid. Having a column pump pressure at …

Phospholipid Membrane Remodeling Through Exogenous Fatty Acid Incorporation In Certain Bacterial Species, Josh Herndon

Honors Theses

Multi-drug resistant bacteria have become problematic in healthcare settings. Recent studies have documented the ability of some bacteria, such as Vibrio species, to assimilate exogenous fatty acids into their membrane phospholipids. Therefore, the current research was performed to determine whether the three virulent, multi-drug resistant bacteria Acinetobacter baumannii, Klebsiella pneumoniae, and Escherichia coli can remodel their cell membranes following exposure to a range of exogenous polyunsaturated fatty acids (PUFAs). Furthermore, we hypothesized that PUFAs would influence phenotypes associated with growth and virulence. Extracted phospholipids were examined by UPLC/MS analysis to confirm assimilation of exogenous PUFAs into the bacterial phospholipids. A. …

Sds-Page Analysis Of Modified Lysozyme By Substituted Benzoquinones And Naphthoquinones, Neethu Kurien

Honors Theses

Quinones are molecules that are commonly found in the environment, as cofactors for proteins or an electron carrier in the mitochondrial electron transport chain. However, quinones also can come from polycyclic aromatic hydrocarbons as their metabolites, harming cellular integrity. In this study, we investigated protein modification of lysozyme in the presence of substituted benzoquinones and naphthoquinones. To simulate physiological conditions, all reactions used phosphate buffer (50.0 mM). While the majority of the experiments were performed at 37 C and pH 7.0, there were also temperature dependence (27 C and 42 C) and pH dependence (6.0 and 8.0) reactions included. SDS-PAGE …

Polymer Nanocomposites Containing High Aspect Ratio Particulates: Innovation In Co-Extruded Multilayer Barrier Films, Kevin Meyers

Dissertations

Delaminated montmorillonite (MMT) clay/ maleic anhydride grafted LLDPE nanocomposite multilayer films with alternating layers of LDPE were produced through multilayer co-extrusion. The MMT concentration within the nanocomposite layers was increased through annealing the films in the melt due to a mismatch in interdiffusion rates of the polymer layers. Analysis of the nanocomposite layers upon annealing revealed that the platelets impinged upon one another resulting in significant improvement in oxygen barrier in the multilayer system, exceeding the results of bulk nanocomposites.

Model analysis demonstrated that increasing the nanoplatelet aspect ratio or initial concentration in the filled layers would lead to even …

Photoelectrochemical Studies On Non-Noble Metal Based Catalysts Towards Tandem Solar Water Splitting, Arun Siddarth Sridhar

Dissertations

Photoelectrochemical (PEC) water splitting makes direct use of solar energy incident on semiconductor photoelectrodes, and it is a convenient, economic option to produce high purity hydrogen at low temperatures. The use of multiple light absorbers can increase overall solar energy utilization and provide a solution to the trade-off between overall band gap and band edge positioning of photoelectrodes specific to solar water oxidation and water reduction. The study of non-noble metal based catalysts for hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) are essential for economic practical commercialization of photo-electrolyzers. This dissertation focuses on the use of a variety …

Genetically Engineered Peptides For Light Harvesting And Folding Kinetics Studies, Aileen M. Eagleton

Chemistry

The preparation and characterization of β-sheet forming polypeptides for use in light harvesting applications is described. The Higashiya genetic cassette strategy (HGCS) was employed in order to make DNA libraries of repetitive DNA sequences. These DNA libraries contained gene cassettes coding for proteins designed to fold into the desired secondary motif. The conditions required for peptide expression, folding and formation of micron length fibrils was determined for the purpose of photophysical characterization, such as fluorescence lifetimes and acceptor dye quantum yields. Of special interest was the investigation of an “antenna effect” under FRET illumination, the intensity of acceptor dye emission …

Experimental And Computational Studies Of Rotation And Proton Tunneling In Organic Molecules And Molecular Dimers, Agapito Serrato Iii

Theses and Dissertations

An introduction to the relations of classical and quantum mechanics are presented in brief. As is an overview of the instrumentation and quantum chemical analysis performed to characterize the molecules presented in in this thesis. The pure rotational spectrum of 3,3,3-trifluoro-2(trifluoromethyl)propanoic acid, perfluorobutyric acid–formic acid dimer, and tropolone–formic acid dimer were measured using high-resolution microwave spectroscopy. The spectra have been observed using a cavity-based Fourier-transform microwave (FTMW) spectrometer and/or a chirped-pulse FTMW.

Microwave-Assisted Ring-Opening Polymerization Of Poly(Ε-Caprolactone), Nancy Obregon

Theses and Dissertations

Poly(ϵ-caprolactone) (PCL) is a biodegradable polyester notorious by its promising properties and applications in the biomedical field. In this work, microwave-assisted ringopening polymerization (ROP) of ϵ-caprolactone (ϵ-CL) was performed. Stannous octoate [Sn(Oct)2] was used as catalyst with and without an alcohol initiator. The different initiators tested were glycerol, diethylene glycol (DEG) and poly(ethylene) glycol (PEG). Aiming to establish reaction parameters, the influence of different reaction times, temperatures, and monomer:initiator:catalyst ratios were examined. It was observed that the reaction was obtained and high molecular weight PCL was achieved successfully without an initiator. However, mixed results were obtained using an initiator. Products …

Kinetics And Activation Energy Parameters For Hydrolysis Of Acetic Anhydride In A Water-Acetone Cosolvent System, Samson Olowoyo

Electronic Theses and Dissertations

The hydrolysis of acetic anhydride is a widely-studied liquid phase reaction studied since 1906. Different approaches have been used to study the kinetics of this reaction. Approaches used by researchers have involved the use of sophisticated experimental set-ups. In this work, the pH technique has been adopted which involves the use of a pH meter to monitor the hydrolysis reaction. Analysis of the hydrolysis reaction has been performed for water/acetone cosolvent systems over a range of temperatures and mole fractions. Eyring analysis was performed under isomole fraction conditions and activation enthalpy, entropy, and Gibbs free energy for hydrolysis of acetic …

Eyring Activation Energy Analysis Of Acetic Anhydride Hydrolysis In Acetonitrile Cosolvent Systems, Nathan Mitchell

Electronic Theses and Dissertations

Acetic anhydride hydrolysis in water is considered a standard reaction for investigating activation energy parameters using cosolvents. Hydrolysis in water/acetonitrile cosolvent is monitored by measuring pH vs. time at temperatures from 15.0 to 40.0 °C and mole fraction of water from 1 to 0.750. This work utilizes a temperature controlled water bath and a Vernier glass-body pH probe with Vernier Logger Pro 3.10.1 software for automated data collection. Data analysis is used to determine observed kinetic rate constants under the assumption that hydrolysis is a pseudo-first-order reaction. Eyring plots were used to compare activation energy parameters under iso-mole fraction conditions. …

Highly Flame Retardant And Bio-Based Rigid Polyurethane Foams Derived From Orange Peel Oil, Chunyang Zhang

Electronic Theses & Dissertations

Polyurethane is an important class of polymer which is being used for various industrial applications in the form of rigid foams, flexible foams, thermoplastic, elastomer, coating, and adhesive. Especially there is a huge market for rigid polyurethane foams for their applications as thermal insulating material in building and housing. In general, polyurethanes are prepared using polyols and diisocyanates. Most of the polyols used by industries are petrochemical based. In this project, a novel polyol from an orange peel oil-based derivative, limonene dimercaptan, was synthesized using one step photochemical thiol-ene reaction. The synthesized polyol was used to prepare flame retardant polyurethane …

The Effects Of Passive Integrated Transponder Tagging On Cortisol Release In The Gulf Killifish, Fundulus Grandis, Ariel Marcelo Hernandez

Senior Honors Theses

Due to its ease of use, low cost, and essentially limitless number of unique codes, PIT tagging has become the favored technique for tagging individuals in biological studies. However, studies employing PIT tagging generally assume that stress due to the implantation and presence of a PIT tag has no influence on the experimental results. This study investigated the effects of PIT tagging on levels of the stress hormone cortisol in the Gulf Killifish, Fundulus grandis, an estuarine fish of the Gulf of Mexico that is prone to daily or seasonal environmental stressors. Cortisol was measured non-invasively by extracting and …

Elucidating Molecular Interactions Of Shigella Type Three Secretion System Components Critical For Pathogenesis, R. Alan Burgess

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Shigella are pathogenic bacteria which commonly infect human hosts through the fecal-oral route. As the causative agent of shigellosis, a disease characterized by severe diarrhea, nausea, and vomiting, Shigella are responsible for an estimated 90 million infections and 100,000 deaths each year. With the emergence of antibiotic resistant strains of Shigella, the need for alternative treatments methods has become critical to fighting outbreaks of shigellosis and drug resistant strains. One such method is to target the infection system of the bacteria, called the type three secretion system (T3SS). The T3SS includes a complex needle and syringe-like apparatus that is …

Tmsotf Assisted Synthesis Of 2’-Deoxy-2’-[18f] Fluoro-Β-D-Arabinofuranosylcytosine ([18f] Fac), Kishore K. Gangangari, John L. Humm, Steven M. Larson, Naga Vara Kishore Pillarsetty

Publications and Research

[¹⁸F]FAC (2’-deoxy-2’-[¹⁸F]fluoro-β-D-arabinofuranosylcytosine, 1) is a versatile probe for imaging deoxycytidine kinase (dCK) expression levels in vivo. dCK is responsible for phosphorylation of deoxycytidine (dC, 2) and other nucleoside analogs, plays a key role in immune activation and has demonstrated to be one of the key enzymes in activating nucleoside based drugs including gemcitabine. Reported synthesis of [¹⁸F]FAC is high yielding but is quite challenging requiring bromination using HBr and careful drying of excess HBr which is critical for successful synthesis. Here in we report a simplified trimethylsilyl trifluoromethanesulfonate (TMSOTf) assisted synthesis …

Synthesis And Characterization Of Biodiesel Fuels From Furfuryl Alcohol And Spent Coffee Grounds, Amanda Raley

Electronic Theses and Dissertations

ABSTRACT

Biodiesel can be synthesized using several different triacylglycerides, alcohols, and catalysts. In this study, fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs) were produced from their respective alcohols and coffee oil, using either a basic (K₂CO₃) catalyst or an acidic catalyst (H₂SO₄). Fatty acid furfuryl esters (FAFurEs) were produced using commercially-purchased cooking oils (canola, olive, corn, sunflower, and peanut) with furfuryl alcohol, a basic (K₂CO₃) catalyst, a co-solvent (THF), and an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate). All samples were produced using either conventional heating methods …

Singlet Oxygen Oxidation Of Guanine, 9-Methylguanine And Guanine-Cytosine Base Pair: Dynamics And Kinetics Revealed By Parallel Gas- And Solution-Phase Experiments And Computations, Wenchao Lu

Dissertations, Theses, and Capstone Projects

Singlet oxygen (¹O₂) oxidatively generated damage of DNA gives rise to mutagenesis, carcinogenesis, and cellular death. Guanine is the most susceptible DNA target of ¹O₂. The related process has been studied over three decades but the mechanism has remained elusive. My thesis research has focused on reaction mechanism, dynamics and kinetics of ¹O₂ oxidation of guanine, 9-methylguanine and guanine-cytosine base pair, from the gas-phase bare ions, through hydrated clusters, to aqueous solution. Various techniques have been adapted in the work, including ¹O₂ generation and detection, guided-ion beam tandem mass …

Removal Of Chromium(Vi) And Chromium(Iii) Ions From Aqueous Solution Using Bio-Char Generated From Agricultural Waste Products, Diego Fernando Gonzalez

Theses and Dissertations

Heavy metals are one of the most persistent and prevalent contaminants in the aquatic environment. The removal of chromium from aqueous solution, especially in the hexavalent form is difficult. New technologies, techniques and/or new materials have been designed in order to effectively and efficiently remove chromium from the aqueous environment. The project focuses on the comparison of the effects of pH, time, temperature, binding capacity on bio-char’ generated from agricultural waste produces vs an amino modified derivative of the bio-char. Pineapple skins were dried, ground, sieved, and pyrolyzed to produce a bio-char material. The bio-char was analyzed using FTIR to …

Long-Range Electrostatic Interactions In Gold Catalysis And Fluorinating Reagent Development., Zhichao Lu

Electronic Theses and Dissertations

Our research focus is on applying two long range electrostatic interactions--coulombic interaction between ion pairs and hydrogen bonding—to two tasks: exploring counterion effects in gold catalysis and utilizing hydrogen bonding for fluorinating reagent development. Cationic gold catalysis is considered one of the most important breakthroughs in organic synthesis over the past two decades. A wealth of empirical information on counterion effects is now available regarding homogeneous gold catalysis. However, the rational understanding of the counterion effect on reactivity is still elusive. We proposed a widely applicable model to rationalize the kinetic effect in gold catalyzed reaction. We first solved the …

Elucidation Of Substrate Binding To Photolyase From Sulfolobus Solfataricus Using Isothermal Titration Calorimetry, Amanda Rose Kuerzi

Theses, Dissertations and Culminating Projects

DNA photolyase is a DNA repair enzyme commonly found across the kingdom of life. Binding studies for the hyperthermophilic photolyase derived from Sulfolobus solfataricus (SsPL) may serve to illuminate how DNA photolyase can adapt over a large temperature range. In the first section of this study, the thermodynamics of substrate binding for SsPL in a choline chloride buffer were determined using isothermal titration calorimetry. Using the Counter-Ion Condensation Concept as a model, ionic strength studies were performed to separate the binding interactions into electrostatic, and nonelectrostatic components. The electrostatic interactions do not appear to make a significant contribution to the …

Development Of Microdialysis Probes In Series Approach Toward Eliminating Microdialysis Sampling Calibration: Miniaturization Into A Pdms Microfluidic Device, Randy Espinal Cabrera

Graduate Theses and Dissertations

A new microdialysis sampling method and microfluidic device were developed in vitro. The method consisted of using up to four microdialysis sampling probes connected in series to evaluate the relative recovery (RR) of different model solutes methyl orange, fluorescein isothiocyanate (FITC)-dextran average mol. wt. 4,000 (FITC-4), FITC-10, FITC-20, and FITC-40. Different flow rates (0.8, 1.0, and 1.5 µL/min) were used to compare experimentally observed relative recoveries with theoretical estimations. With increasing the number of probes in series, the relative recovery increases and ~100% (99.7% ± 0.9%) relative recovery for methyl orange was obtained. For larger molecules such as fluorescein isothiocyanate …

Development Of New Useful Methods For Aldehyde Synthesis And Its Application In Synthesis, He Huang

Chemistry and Chemical Biology ETDs

Development of sustainable synthetic technologies for molecular construction is an important but formidably challenging task in modern organic synthesis. Aldehyde synthesis represents a long-standing interest in synthesis because of the synthetic utility. Classic methods for aldehyde synthesis have the drawbacks of the use of harsh reaction conditions, poor atom-economy and multi-step operation, and production of stoichiometric amount of chemical wastes. The state-of-the-art strategies employ transition metal complexes as catalysts to promote formylation reactions. The concerns of catalyst cost, operation complexity and poor functional group tolerance demands more efficient synthetic technologies. My Ph.D. study focuses on design of conceptually novel catalytic …

Photoelectrochemical Investigations On Novel Earth Abundant Solid State Catalysts For Solar Water Oxidation, Nathaniel Branimir Kurtz

Honors Theses

In light of a looming fossil fuel scarcity, many forms of alternative, clean energy production are being researched in order to provide a more sustainable source of energy production for the future. One area of research is on using novel, abundant catalytic materials in conjunction with semiconducting materials to drive the splitting of water in order to produce hydrogen gas, an energy-rich fuel. Currently, efficiency is limited by the energy bottleneck posed by the oxygen evolution reaction (OER) half of water splitting. In this work, cobalt selenide (CoSe) catalyst paired with the semiconductor iron oxide (Fe2O3) has been identified as …

Computational Study Of Lawesson’S Reagent Mediated Fluorenone Dimerization Forming 9,9’-Bifluorenylidene, Andrew Jourdan Eckelmann

Graduate Theses/Dissertations

The ambition of this work is to start a path to the a priori rational design of high yield production for electron acceptors with finely tuned band gaps, from the comfort of an armchair. To this end, organic photovoltaics offer a cheap and sustainable means of manufacture using readily available materials and avoids the toxicity of some of the heavy metals used in first and second-generation solar cells such as cadmium. The microwave assisted Lawesson’s reagent mediated one-pot one-step solventless synthesis takes less than 3 minutes and results in an 84% yield of 9,9’-bifluorenylidene from two equivalents of fluorenone. While …

Errata For Manuscript #34, Carl W. David, Jan Siroky

Chemistry Education Materials

An error in manuscript 34 of this collection concerning the Laplacian in spherical polar coordinates is corrected.

Synthesis Of A Silsesquioxane Based Supramolecular Polymer, Rachel Bianculli

Honors Projects

Research toward smart materials, specifically self-healing polymers, is an expanding topic within the materials science field. These materials rely heavily on dynamic crosslinking that is achieved by inducing different degrees of hydrogen bonding, van der Waals forces, etc. This work, demonstrated by research previously done within the Ostrowski research group, shows how coordination bonds of transition metals have been shown to create light activated, self-healing properties. Work done with these light-activated chromium (III) complexes with a poly(butylyene-co-ethylene) backbone have shown how metal—ligand coordination geometries can tune mechanical properties of the polymeric material. However, these materials suffer from being incredibly soft …

Evaluation Of Cafo Dairy Manure Treatment To Reduce Nutrient Transport, Jenna Laib

Honors Projects

Excess amounts of phosphorus and nitrogen flowing into Lake Erie from agricultural fields in Northwest Ohio has led to several harmful algal blooms (HABs). One potential source of those nutrients is manure applied to fields for fertilizer. Manure from confined animal feeding operations (CAFOs) is 95-98% water with only ~3% solids and nutrients, thus physical transportation is expensive relative to the value of the agricultural nutrients. Furthermore, once manure nutrients are applied to agricultural fields, they are relatively easily mobilized to waterways by precipitation. More than 800 lab-scale tests have been used to optimize the treatment of CAFO manure with …

A Label-Free Immunosensor Based On K3[Fe(Cn)6] And Aldehyde-Functionalized Pyridinium, Xia Hu, You-Ming Shen, Guang-Yu Shen

Journal of Electrochemistry

A novel aldehyde-functionalized pyridinium was successfully synthesized. Using K₃[Fe(CN)₆] as a redox species modified on the surface of the electrode through Poly(diallyldimethylammonium chloride), we developed a label-free immunosensor based on aldehyde-functionalized pyridinium that was applied to simplify antibody immobilization on the electrode surface, in which no additional chemical cross-linking was required. In addition, the introduction of K₃[Fe(CN)₆] on the surface of electrode avoided the use of other redox species in the electrolyte solution. Under the optimal experimental conditions, differential pulse voltammetry (DPV) signals corresponding to different α-Fetoprotein (AFP) concentrations were measured. After …