Chemistry Commons^™

The Discovery And Development Of Metal-Free Arylation Reactions With Unsymmetrical Diaryliodonium Salts, Sunil Kumar Sundalam

Dissertations and Theses

Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous amount of research has been published in achieving these chemical transformations using stoichiometric reagents and transition metal-catalyzed reactions. However, challenges still remain. An alternative and comparable methodology to metal-catalyzed reactions to overcome the drawbacks will advance this particular area of research is desirable.

Hypervalent iodine compounds offer a promising approach to metal-free arylation reactions. These mild, air and moisture stable compounds have showed significant success as non-toxic and metal-free reagents …

Characterization Of Reagent Pencils For Deposition Of Reagents Onto Paper-Based Microfluidic Devices, Cheyenne H. Liu, Isabelle C. Noxon, Leah E. Cuellar, Amanda L. Thraen, Chad Immoos, Andres W. Martinez, Philip J. Costanzo

Chemistry and Biochemistry

Reagent pencils allow for solvent-free deposition of reagents onto paper-based microfluidic devices. The pencils are portable, easy to use, extend the shelf-life of reagents, and offer a platform for customizing diagnostic devices at the point of care. In this work, reagent pencils were characterized by measuring the wear resistance of pencil cores made from polyethylene glycols (PEGs) with different molecular weights and incorporating various concentrations of three different reagents using a standard pin abrasion test, as well as by measuring the efficiency of reagent delivery from the pencils to the test zones of paper-based microfluidic devices using absorption spectroscopy and …

Traceable Peo-Poly(Ester) Micelles For Breast Cancer Targeting: The Effect Of Core Structure And Targeting Peptide On Micellar Tumor Accumulation, Shyam M. Garg, Igor M. Paiva, Mohammad R. Vakili, Rania Soudy, Kate Agopsowicz, Amir H. Soleimani, Mary Hitt, Kamaljit Kaur, Afsaneh Lavasanifar

Pharmacy Faculty Articles and Research

Traceable poly(ethylene oxide)-poly(ester) micelles were developed through chemical conjugation of a near-infrared (NIR) dye to the poly(ester) end by click chemistry. This strategy was tried for micelles with poly(ε-caprolactone) (PCL) or poly(α-benzyl carboxylate-ε-caprolactone) (PBCL) cores. The surface of both micelles was also modified with the breast cancer targeting peptide, P18-4. The results showed the positive contribution of PBCL over PCL core on micellar thermodynamic and kinetic stability as well as accumulation in primary orthotopic MDA-MB-231 tumors within 4–96 h following intravenous administration in mice. This was in contrast to in vitro studies where better uptake of PEO-PCL versus PEO-PBCL micelles …

Nanoparticle-Based Drug-Delivery Systems Studied By Second Harmonic Generation, Raju Ram Kumal

LSU Doctoral Dissertations

Second harmonic generation (SHG) is used to study different types of colloidal nanoparticle drug-delivery systems. The surface charge density, electrostatic surface potentials, and ion adsorptions of 50 nm colloidal gold nanoparticle samples coated with mercaptosuccinic acid are determined using SHG measurements under varying NaCl and MgCl₂ concentrations in water. Numerical solutions to the spherical Poisson-Boltzmann equation are fit to the SHG results to account for the nanoparticle surface curvature and ion adsorption to the Stern layer interface, showing excellent agreement with electrophoretic mobility measurements. In another study, nanoparticles of gold, silver and polystyrene are functionalized with microRNA using a …

Exploration Of A Unique Uranium Mediated Carbon-Carbon Radical Coupling Reaction, Zhengjia Tong, Caleb J. Tatebe, John J. Kiernicki, Matthias Zeller, Suzanne C. Bart

The Summer Undergraduate Research Fellowship (SURF) Symposium

Designing an efficient nuclear fuel cycle has motivated decades of research on aqueous phase uranium chemistry. As such, studies are often limited by the formation of unreactive uranium oxides and/or solubility issues. Carrying out reactions in non-aqueous solvents addresses said problems and enables explorations into previously unattainable reactivity and fundamental properties of uranium. One such feat is the syntheses of uranium alkyls, as they permit research into bond interactions between uranium and carbon. Considering uranium’s oxophilicity, we investigated the relatively understudied uranium(III) alkyls—both their reactivity and reaction mechanism—towards oxygen-containing reagents. In an inert atmosphere, various uranium alkyl complexes were treated …

Synthesis Of Healable Organic Semiconductor Through Dioxaborolane Bond, Junchen Liu, William W. Mcnutt, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

The field of organic semiconductors have gained enormous attention the past few decades. Organic materials offer numerous advantages over their inorganic counterparts. Recently a number of works have demonstrated organic semiconductors with healable properties. We aim to investigate the healable ability of an organic semiconductor by mimicking a vitrimer system through the reversible dioxaborolane bond. Vitrimers are polymers with reversible crosslink system. It has been reported that the use of the borane-oxygen bond as the crosslink showed good mechanical performance. The electrical properties will be inspected for the vitrimer-like polymer. In this report we describe a Diketopyrrolopyrrole base polymer incorporating …

How Strongly Do Oysters Stick?, Nicolás M. Morato, Andrés M. Tibabuzo, Jonathan J. Wilker

The Summer Undergraduate Research Fellowship (SURF) Symposium

Biological adhesives are a type of interfacial material that has incredible potential to generate new biomimetic compounds that can replace current strong, but toxic, adhesives. Therefore, a study of the chemical composition and mechanical properties of those bio-adhesives is necessary. However, in the case of oysters, despite known chemical characterization of the adult’s adhesive, there are almost no studies on its mechanical properties. Furthermore, there is no available information on the adhesive properties of spat (oysters in their larvae state). Herein, we present the first mechanical characterization of the spat adhesive, measuring its adhesion strength by hydrodynamic determination using a …

Raman Spectroscopy Of Oxygen Evolution Catalysts And Psii Manganese Model Compounds, Sergei Shmakov, Daniel A. Hartzler, Alireza Karbakhsh Ravari, Yulia Pushkar

The Summer Undergraduate Research Fellowship (SURF) Symposium

Photosynthesis is the basis of life on earth, and oxygen evolution catalysts are key components of this complicated, yet not fully understood process. Photosystem II, a large membrane bound pigment-protein complex, is the key system that facilitates oxygenic photosynthesis via the oxygen evolving complex (a natural oxygen evolving catalyst). It is a key component in oxygen producing catalysts, which can be used in fields such as energy production and biomimetic catalysts. The oxygen evolution cycle, or Kok cycle going within it is still not studied completely. In this project, we were studying the vibrational (and structural) state of a Manganese …

Mobility Characteristics Of Azithromycin In Soil, Ryan Minter, Jihyun Kim, Linda Lee

The Summer Undergraduate Research Fellowship (SURF) Symposium

The presence of pharmaceutical and personal care products (PPCPs) in the environment has become a widespread problem in recent decades. Azithromycin, a macrolide antibiotic commonly prescribed for infections in humans, has been detected in waste treatment plant discharge and surface waters across the world. Data on the mobility characteristics of azithromycin in soil is scarce, and further studies must be performed to explore the potential for azithromycin leaching to groundwater or becoming available for plant uptake. In this study, azithromycin sorption isotherms were measured on eight soils varying in pH, organic carbon content, and clay content. Soil was equilibrated with …

Applying Machine Learning To Computational Chemistry: Can We Predict Molecular Properties Faster Without Compromising Accuracy?, Hanjing Xu, Pradeep Gurunathan, Lyudmila Slipchenko

The Summer Undergraduate Research Fellowship (SURF) Symposium

Non-covalent interactions are crucial in analyzing protein folding and structure, function of DNA and RNA, structures of molecular crystals and aggregates, and many other processes in the fields of biology and chemistry. However, it is time and resource consuming to calculate such interactions using quantum-mechanical formulations. Our group has proposed previously that the effective fragment potential (EFP) method could serve as an efficient alternative to solve this problem. However, one of the computational bottlenecks of the EFP method is obtaining parameters for each molecule/fragment in the system, before the actual EFP simulations can be carried out. Here we present a …

Parallelization Of Molecular Docking Algorithms Using Cuda For Use In Drug Discovery, Brandon Stewart, Jonathan Fine, Gaurav Chopra Phd

The Summer Undergraduate Research Fellowship (SURF) Symposium

Traditional drug discovery methodology uses a multitude of software packages to design and evaluate new drug-like compounds. While software packages implement a wide variety of methods, the serial (i.e. single core) implementation for many of these algorithms, prohibit large scale docking, such as proteome-wide docking (i.e. thousands of compounds with thousands of proteins). Several docking algorithms can be parallelized, significantly reducing the runtime of the calculations, thus enabling large-scale docking. Implementing algorithms that take advantage of the distributed nature of graphical processing units (GPUs) via the Compute Unified Device Architecture (CUDA) enables us to efficiently implement massively parallel algorithms. Two …

Temperature-Dependent Exciton Dynamics Of Superacid Treatment In Monolayers Of The Metal Dichalcogenide Mos2, Mingwei Zhou, Long Yuan, Jordan Snaider, Libai Huang

The Summer Undergraduate Research Fellowship (SURF) Symposium

To improve optoelectronic semiconductor materials, one of the most efficient research areas is the two-dimensional (2D) transition-metal dichalocogenides (TMDCs). It has been shown that organic nonoxidizing superacid bis(trifluoromethane)sulfonamide (TFSI) treatment of molybdenum disulfide (MoS₂) monolayer could uniformly enhance its photoluminescence by more than two orders of magnitude and also extend the lifetime of excitons. This could greatly improve the efficiency of the solar energy usage, but the mechanism behind it has not been fully understood. Extreme low temperatures (approximately 7K), which slow the surface exciton mobility, were applied to investigate the changes of treated MoS₂ monolayer surfaces. …

Usage Of Fomblin Y To Improve Water Repellence Of Surface Coatings, Shawn Pj Kirby, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Fluoro-Decyl POSS (FDP) has shown strong potential as a water repellant surface coating. Additionally, Fomblin is a solvent believed to have the ability to control the crystallization of POSS compounds on surfaces. Controlling the crystallization is key to improving water repelling abilities of surfaces. Thus, dip coating FDP and Fomblin onto surfaces is being investigated for water repulsion, mechanical stability, and deposition feasibility. First, temperature dependence of solubility of Fluoro-Decyl POSS in Fomblin was tested using Dynamic Light Scattering. Relative water repelling abilities of different coatings were determined by measuring contact angle of surfaces with water. Coatings with and without …

Comparative Solubility Of Poss Compounds In Fomblin Y, Shawn Pj Kirby, Jeffrey Alston, Andrew Guenthner

STAR Program Research Presentations

Fluoro-Decyl POSS (FDP) has shown strong potential as a water repellant surface coating. Additionally, Fomblin is a solvent believed to have the ability to control the crystallization of POSS compounds on surfaces. Controlling the crystallization is key to improving water repelling abilities of surfaces. Thus, dip coating FDP and Fomblin onto surfaces is being investigated for water repulsion, mechanical stability, and deposition feasibility. However, in order for this to be successful, POSS must be soluble in Fomblin. Temperature dependence of solubility of Fluoro-Hexyl, Fluoro-Octyl, Fluoro-Decyl POSS in Fomblin was tested using Dynamic Light Scattering. The values were compared, and it …

Exploring Flexible Configurations Of A Custom Multipath Lc –Ms For Small Molecules And Protein Analysis, Dananjaya Kalu Appulage

Chemistry & Biochemistry Dissertations - Archive

There are diseases where both small molecules and proteins are found as disease indicators. In the usual analysis of small molecules, proteins are precipitated out during the sample preparation. In the small molecule quantitation, triple quadrupole mass spectrometers (QqQ- MS) are commonly used even in the clinical lab settings. Even though QqQ is giving only unit resolution, it is highly sensitive and specific specially when it is used in the multiple reaction monitoring (MRM) mode. In the liquid chromatography method development, automation of column and mobile phase screening could save significant amount of operators’ time. The use of Shimadzu Nexera …

F₄₂₀ Cofactor Dependent Enzymes : Kinetic, Mechanistic And Structural Characterization Of F₄₂₀-Dependent Glucose-6-Phosphate Dehydrogenase (Fgd) From Mycobacterium Tuberculosis, Mercy A. Oyugi

Chemistry & Biochemistry Dissertations - Archive

F₄₂₀-dependent glucose-6-phosphate dehydrogenase (FGD) from Mycobacterium tuberculosis (Mtb) is one of a few enzymes that utilize the unique F₄₂₀ cofactor for catalysis. FGD catalyzes the first committed step of the pentose-phosphate pathway, where it uses the oxidized F₄₂₀ cofactor to convert glucose-6-phosphate (G6P) to 6-phosphogluconolactone. Mtb is the bacteria that causes Tuberculosis (TB), which is currently the world’s deadliest bacterial disease. The pentose-phosphate pathway is important for survival of Mtb, since it provides precursors for nucleic acid synthesis and yields reducing equivalents that are essential for other metabolic pathways. The fact that FGD catalyzes the committed step of the pentose-phosphate …

Development Of Ultrahigh Performance Chiral Phases For Separations Approaching The Speed Of Sensors, Darshan C. Patel

Chemistry & Biochemistry Dissertations - Archive

Chromatography using chiral stationary phases is the most effective and popular technique for qualitative and quantitative analysis of enantiomers in the pharmaceutical, agricultural, and food industry, among many others. Given the prevalence of chirality in nature, creation of new technologies for improving the speed and performance of chiral separations can provide immediate and significant benefits. This dissertation focuses on development of ultrahigh performance chiral phases which can provide separations at speeds that approach the speed of typical sensors and thereby enable chromatography as a real-time analysis tool. A variety of chiral selectors namely macrocyclic glycopeptides (teicoplanin, teicoplanin aglycone, vancomycin), cyclic …

Epigenetic Mechanism Of Regulation Of Hox Genes And Neurotransmitters Via Hormones And Lncrna, Paromita Deb

Chemistry & Biochemistry Dissertations - Archive

Endocrine disrupting chemicals (EDCs) are classes of environmental contaminants whose exposure even at very low concentrations interfere with normal endocrine signaling and induce many adverse health effects including increased risk of birth defects, diabetes, obesity, abnormal reproduction, and cancer. EDC exposure alters the epigenetic programming of cells resulting in altered gene expression and regulation and cell signaling. These EDCs include bisphenol-A (BPA), diethylstilbesterol (DES), polychlorinated biphenyl (PCB), phthalates, phytoestrogens, methoxychlor, fungicides, insecticide, herbicide, and some heavy metals. As a part of my work, I have investigated epigenetic impacts of EDCs on HOX (homeobox containing genes) genes, which are critical players …

Enrichment And Identification Of Disulfide Bonded Peptides By Tandem Mass Spectrometry, Pooja Rajeshbhai Ramanuj

Chemistry & Biochemistry Theses - Archive

Proteins are Comprised of different amino acids which can undergo various modifications known as post-translational modifications (PTMs). Amino acid’s side chains are the most common sites for the PTMs. Cysteine side chain can undergo several PTMs and one very common one is disulfide bond formation. Disulfide bond aids in maintaining protein tertiary structures, its identification is an inevitable aspect in studying protein functions. Furthermore, disulfide bonds are potential targets to develop new protein therapeutics for life-threatening diseases such as cancer. Literature surveys revealed several methods to identify disulfide bonds, which require either high quality sample or are highly laborious. Moreover, …

Toxicity Study Of Cace₂S₄, Wafa Tonny

Chemistry & Biochemistry Theses - Archive

In recent years, rare earth sulfides have received attention for their interesting thermoelectric and optical properties.1 They exhibit a fairly wide range of colors, which makes them promising candidates as pigments.2 The demand for red colored pigments in industrial application is high but the current ones in use are not environmentally friendly. This has garnered attention towards the rare-earth sulfides. Among the rare-earth sulfide compounds, Ce₂S₃ is a highperformance pigment of red color. It is particularly interesting as doping with alkaline earth metal stabilizes the structure of Ce₂S₃ at low temperature and plays a role in tuning its color from …

Aryl Transfer Selectivity In Metal-Free Reactions Of Unsymmetrical Diaryliodonium Salts, David Stuart

Chemistry Faculty Publications and Presentations

Aromatic rings are found in a wide variety of products, including pharmaceuticals, agrochemicals, and functional materials. Diaryliodonium salts are novel reagents used to transfer aryl groups under both metal-free and metal-catalyzed reactions and thereby synthesize arene-containing compounds. This review focuses on recent studies in selective aryl transfer reactions from unsymmetrical diaryliodonium salts under metal-free conditions. Reactions reported from 2008 to 2017, which represents a period of significant growth in diaryliodonium salt chemistry, are presented and organized by the type of reactive intermediate formed in the reaction. Specifically, reactions involving λ³-iodane, λ³-iodane radical anions, aryl radicals, and …

Plasminogen Activator Inhibitor-1 Inhibitors And Methods Of Use Thereof, Daniel A. Lawrence, Cory Emal, Ashley Reinke, Shih-Hon Li, Mark Warnock, Gregory Abernathy*

Patents

The invention relates to plasminogen activator-I (PAI-1) inhibitor compounds and uses thereof in the treatment of any disease or disorder associated with elevated PAI-1. The invention includes, but is not limited to, the use of such compounds to prevent or reduce thrombosis and fibrosis, to promote thrombolysis, and to modulate lipid metabolism and treat diseases or disorders associated with elevated PAI-1, cholesterol, or lipid levels.

Electrokinetically Operated Integrated Microfluidic Devices For Preterm Birth Biomarker Analysis, Mukul Sonker

Theses and Dissertations

Microfluidics is a vibrant and expanding field that has the potential for solving many analytical challenges. Microfluidics shows promise to provide rapid, inexpensive, efficient, and portable diagnostic solutions that can be used in resource-limited settings. Microfluidic devices have gained immense interest as diagnostic tools for various diseases through biomarker analysis. My dissertation work focuses on developing electrokinetically operated integrated microfluidic devices for the analysis of biomarkers indicative of preterm birth risk. Preterm birth (PTB), a birth prior to 37 weeks of gestation, is the most common complication of pregnancy and the leading cause of neonatal deaths and newborn illnesses. In …

Crispr/Cas9 In Leishmania Genome Editing : Towards A Proof Of Concept, Zein Kasbo

Theses, Dissertations and Culminating Projects

Leishmaniasis is a parasitic Neglected Tropical Disease (NTD) that affects mostly poor countries of the third word due to their limited access to clean water and health care. The disease is transmitted through the bite of a sand fly of the genus Phlebotomus in the Old World, and of the genus Lutzomyia in the New World. Historically, NTDs have not been given adequate attention or research funding and finding curative treatments has been slow. However, the fact that the insect vector and the parasite can live and thrive in any ecological system in the world, and under the current circumstances …

Renewed Significance Of Ras Gtpases, Michael Wey

Chemistry & Biochemistry Dissertations - Archive

The Ras superfamily of GTPases act as molecular switches and play a critical role in intracellular signal transduction. These GTPases cycle between an active GTP- bound form and an inactive GDP-bound form to regulate a myriad of cellular processes. However, this classical model of Ras regulation does not accurately project the entire picture of Ras regulation. This work discusses non-classical and newly discovered elements of the Ras signaling network. While intrinsic kinetic properties of Ras are included in the classical model of Ras regulation, the importance of them is understated. We show that the development Costello Syndrome from somatic Harvey …

Geochemical Fractionation, Speciation, And Bioavailability Of Heavy Metals In Stream Sediments In Aurora, Mo, Miles Pearson

Graduate Theses/Dissertations

Stream sediments from Chat Creek in Aurora, MO, part of the former Tristate Mining District, were digested via a sequential extraction procedure modeled after the Tessier method. Prior sampling had shown elevated levels of zinc, lead, and cadmium in sediments located near former chat piles. Metals in sediments were divided into four geochemical fractions: 1) easily exchangeable, 2) carbonate-bound, 3) iron-manganese oxides-bound, and 4) organic matter-bound. The distribution of the metals within these fractions can help predict the bioavailability and speciation of said metals. The majority of metals were contained in the third and to a lesser extent the fourth …

Chlorate Formation In On-Site Hypochlorite Generation Facilities: Effects Of Temperature, Ph, And Storage Times, Lukas Simon Kriem

Graduate Theses/Dissertations

Drinking water is one of the fundamental pillars of modern society, and it is crucial that pathogen-free drinking water be provided to communities. Currently, one third of all drinking water in the U.S. is being disinfected using hypochlorite and the number is rising. However, use of hypochlorite is facing the issue of a hypochlorite byproduct, chlorate ion, which at high concentrations is considered a health risk to humans. During and after its electrolytic generation process, hypochlorite may go through a disproportionation reaction to form chlorate and chloride, a process which is thermodynamically favored. Even though chlorate in drinking water is …

Investigating Hydrothermal And Radiation Effects On Nitrogen Heterocycles Relevant To Meteorite Parent Bodies, Phillip G. Hammer

Boise State University Theses and Dissertations

Organic compounds in meteorites were likely transformed by a variety of processes on the asteroid parent body including aqueous, thermal, and radiolytic alteration. Previous studies have identified a suite of purine nitrogen heterocycles in carbonaceous chondrites (a class of meteorites) and determined that their likely origin was due to cyanide chemistry. The thesis research described here consisted of two parts: investigating thermal effects on aqueous ammonium cyanide reactions and the production/survivability of organics (Chapter 2) and investigating gamma radiation effects on purine nitrogen heterocycles to understand how prolonged radiation exposure influenced the distribution and abundance of nitrogen heterocycles measured in …

Electrogenerated Chemiluminescent Studies Of 9,10-Diphenylanthracene, Rubrene, Tris(2,2'-Bipyridine)Ruthenium(Ii) Species, And Their Derivatives For Sensitive Detection Of Biomolecules, Pradip Bastola

Dissertations

This dissertation explored and investigated the coreactant electrogenerated chemiluminescent (ECL) properties of unmixed and mixed systems of highly efficient ECL emitters, such as 9,10-diphenylanthracene (DPA), rubrene (RUB), and tris(2,2′-bipyridine)ruthenium(II) [(Ru(bpy)₃²⁺)] species as well as their water-soluble derivatives, which can serve as ECL labels for sensitive bioanalysis of single or multiple analytes. The screening of most favorable common ECL coreactants, their concentration effects along with the effect of working electrode materials on ECL behavior, and energy transfer related interactions between ECL emitters were systematically investigated. In addition, a strategy for improvement of ECL signals with the use of …

Cellulose Reinforced Thermoplastic Composites By In-Situ Ring-Opening Polymerization, Shahab Kashani Rahimi

Dissertations

Over the past two decades, the increasing concern about the negative environmental impacts of synthetic materials has led to rising interests in utilizing renewable natural resources to develop polymer materials with comparable properties and performance to their synthetic counterparts. One of the major fields of interest is polymer composites where the replacement of synthetic fibers with bio renewable natural fibers is of great potential. However, the processing difficulties, in terms of fiber dispersion and thermal stability have limited the application of cellulosic fibers to polymers with low processing temperatures which are mostly hydrophobic polymers. As a result, the true reinforcing …