Physical Sciences and Mathematics Commons^™

1,2-Diazetidine As A New Amidomethylative Reagent To Control The Selectivity For The Synthesis Of N-Heterocycles And Ru(Ii)-Catalyzed Enantioselective Hydroarylation To Form Chromane Derivatives, Chaminda Lakmal Hetti Handi

Theses and Dissertations

1,2-Diazetidine is a four-membered ring heterocyclic compound which has two adjacent nitrogen atoms. However, the syntheses of C-unsubstituted 1,2-diazetidines are rarely reported in the literature. C-unsubstituted 1,2-diazetidines were synthesized through an operationally simple intermolecular vicinal disubstitution reaction between 1,2-dibromoethane and hydrazine with N-arylsulfonyl as the protecting group. Several different types of C-unsubstituted 1,2-diazetidines derivatives were synthesized with either two of the same or two different N-arylsulfonyl groups. The electronic and steric properties were analyzed using Raman spectroscopy and computational calculations. Then, several synthetic applications were demonstrated with 1,2-ditosyl-1,2-diazetidine (DTD). As a synthetic application, a nucleophilic ring-opening reaction of the diazetidine …

Synthesis And Characterization Of A Ccc-Nhc Manganese Complex And Its Catalytic Activity In Alpha-Alkylation Reactions Of Ketones Using Alcohols – Acceptorless Dehydrogenative Coupling Reaction, Thi Bao Tran Nguyen

Theses and Dissertations

N-heterocyclic carbenes are essential for the synthesis and stabilization of various metal complexes due to the tendency to act as sigma-donor of sp2 hybridized lone pair in carbene into sigma-accepting orbital of metals. Meanwhile, the electronic and steric properties of pincer complexes can be fine-tuned by modifying three sites bonded to the metals. Utilizing advantages of both NHCs and the pincer structures, NHCs-based pincer complexes have become increasingly developed in recent years. After the discovery of zirconium and rhodium complexes with CCC-NHC backbones reported in 2005, Hollis’s group has been interested in applying the CCC-NHC pincer precursor for other transition …

Disease Biomarker Discovery And Fungal Metabolites Extraction Protocol Optimization Using Gcms Based Metabolomics, Chathuri Udeshika Gamlath Mohottige

Theses and Dissertations

Metabolomics is a powerful science that can be applied for the discovery of disease biomarkers, and investigation of altered metabolomes due to abiotic and biotic perturbations. This dissertation is focused on untargeted metabolomic applications to investigate fungal metabolite alterations associated with pathogenicity, fungal disease propagations, and symbiosis. This dissertation employs qualitative analysis of metabolite mixtures using HS-SPME coupled GC-MS and TMS derivatization followed by GC-MS analytical platforms. In the first study, we discovered a biomarker combination to diagnose fungal soft tissue disease in sweet potato at an early stage of disease propagation. We used an HS-SPME GC-MS untargeted metabolomics workflow …

Characterization Of Small Molecules And Ions By Atmospheric Pressure Ionization-Mass Spectrometry, Maleesha De Silva

Theses and Dissertations

Mass spectrometry (MS) has become a widely used technique for the characterization of a wide range of substances in diverse fields. The selection of appropriate ionization techniques, source parameters, charge carriers based on the analyte’s polarity is essential in MS as only the ions are detected. When using a soft ionization technique, single stage-MS at best provides only chemical composition; thus, tandem MS is needed to determine structural information and dissociation pathways. This dissertation focuses on the characterization of various small molecules and ions using different ionization techniques, charge carriers, and collision-induced dissociation (CID).

In Chapter II, commercially available ionic …

Construction Of Fluorescent Helicase Fusion Proteins For Use In Fret Studies On Helicase Function And Stoichiometry, Moneer Arabiyat

Theses and Dissertations

This thesis details the construction of N-terminal fusions of the E. coli helicase DnaB to fluorescent proteins mT-Sapphire and mVenus, and of C-terminal fusions of the hepatitis C virus NS3 helicase (NS3h) to mT-Sapphire and mVenus. These fluorescent fusion proteins were constructed to be used in FRET studies of helicase function and stoichiometry. One example is in assessing the potential oligomerization and cooperativity of NS3h protomers in unwinding RNA. Another potential use is in assessing the stoichiometry of the replisome of E. coli; older studies support a dimeric polymerase model of the replisome. Recent studies however suggest that an active …

Electrospun Polyetherimide And Polybenzimidazole Fibers And Composites, Fatema Ha-Mim Binta Hafiz

Theses and Dissertations

In this study, polymer micro- and nanocomposite fibers with PBI and PEI as polymer, and exfoliated graphite and nitroxide-functionalized graphene oxides have been prepared. Electrospinning has been chosen as a fiber processing technique. This work describes the electrospinning process of the mentioned polymer fibers and composite fibers followed by their characterization by XRD, ATR, SEM, TGA, DSC and Tensile testing.

Flexible Quantum Dot Solar Cell With Nanostructure Titanium Dioxide Photoanode With Modified Counter Electrode, Haimanti Majumder

Theses and Dissertations

Because of unique photovoltaic properties, nanostructured morphologies of TiO2 on flexible substrate have been studied widely in recent years in dye-sensitized solar cells (DSSCs). Nanostructured electrode materials with high surface area can promote rapid charge transport and thus improve the light-to-current conversion efficiency. Herein, this project generates an improved photoanode with forest like photoactive TiO2 hierarchical microstructure using a simple and facile hydrothermal route. To improve the photocurrent efficiency, PbS quantum dot has been applied in different thicknesses to evaluate the best performance. The deposition of quantum dot was done by easy SILAR cycle. Four different SILAR cycle has been …

Synthesis, Isolation And Structural Elucidation Of Cage-Shaped Aluminum And Gallium Phosphorous Aryloxide Complexes As Highly Reactive Lewis Acids And Carboxyboranes As Carbon Monoxide Releasing Molecules (Corms), Hussam Wannas Shinawa Alhamza

Theses and Dissertations

Group 13 Lewis acids have gained a lot of interest in over the years due to their reactivity, potency, and applications in the field of catalysis. Generally, there is a direct relationship between the catalytic activity of the organometallic Lewis acid and its acidity. However, this gives rise to a bigger challenge which is related to the stability of the catalyst. Our preliminary results from working on the catalytic reduction of CO2 have shown catalytic deactivation after one or two cycles. Utilizing bulkier substituents such as monodentate phenolates have shown promising increased stability and reactivity. The structural optimization (i.e., open-shape …

Functional Material Systems For Stimuli-Responsive Interference Coloration, Milad Momtaz

Theses and Dissertations

Part I: Responsive Interference Coloration (RIC) Systems for High-Performance Humidity Sensing

High-humidity conditions (85−100% relative humidity) have a variety of effects on many aspects of our daily lives. In spite of significant progress in the development of structural coloration-based humidity sensors, enhancing the sensitivity and visual humidity resolution of these sensors at high-humidity environment remains a big challenge. In this work, high-performance colorimetric humidity sensors based on environment-friendly konjac glucomannan (KGM) are introduced. These sensors are fabricated via thin-film interference and prepared using a simple, affordable, and scalable method. An effective approach is shown for markedly improving the sensitivity and …

Part I: A Concise Synthesis Of Microtubule Inhibitor Tryprostatin A And B And Its Analogs Part Ii: Brønsted Acid Catalyzed Reactions Of Aromatic Ketones With Ethyl Diazoacetate And Its Synthetic Scope, Khorshada Jahan

Theses and Dissertations

PART I: A CONCISE SYNTHESIS OF MICROTUBULE INHIBITOR TRYPROSTATIN A AND B AND ITS ANALOGSMicrotubules are promising targets for treating cancer by stopping the cell division in mitosis(M). Tryprostatins A and B (TPS A and B) are one of the important alkaloids for treating cancer, via microtubule inhibition. Studied found that Tryprostatins A and B act as an antimitotic agent by inhibiting cell cycle progression of tsFT210 cells in the G2/M phase at a final concentration of 50 µg/ml of TPS A and 12.5 µg/ml of TPS B, respectively. Usually, Tryprostatins A and B are isolated from natural source Aspergillus …

Mass Spectrometry Directed Pre-Clinical Studies Of Asthma Candidate Midd0301 And Its Analogs, Md Shadiqur Rashid Roni

Theses and Dissertations

ABSTRACTMASS SPECTROMETRY DIRECTED PRE-CLINICAL STUDIES OF ASTHMA CANDIDATE MIDD0301 AND ITS ANALOGS by Md Shadiqur Rashid Roni The University of Wisconsin-Milwaukee, 2021 Under the Supervision of Professor Alexander (Leggy) Arnold

Asthma is one of the most prevalent global health problems. More than 25 million Americans are suffering from asthma and their symptoms especially in children are not well controlled with current medications. The current therapeutic options to control symptoms are limited and are commonly based on inhaled corticosteroids. There are several reasons for uncontrolled asthma symptoms that includes steroid resistance, improper use of inhalers and very few orally available medications. …

Solid Sorbents For Improved Chemical Separations: Applications In Nuclear Medicine And Environmental Remediation, Kevin Wolters

Theses and Dissertations

Solid sorbents have been applied to the separation of radionuclides since the advent of nuclear technology itself. First used for the cleanup and storage of radionuclides remaining from nuclear testing and nuclear power plants, these materials (e.g., inorganic and organic ion-exchange resins) were used to create solid nuclear waste forms as a way of reducing the potential for environmental contamination arising from storage of liquid wastes. The invention of nuclear medicine, which coincided with the introduction of nuclear technology, led to the need for high purity radionuclides for human use. One of the most widely used radionuclides in nuclear medicine …

The Impacts And In-Depth Study Of The Environmental Contaminant, Perfluorooctane Sulfonic Acid, And Its Interactions With Water, Karla Veronica Salazar

Theses and Dissertations

Perfluorooctanesulfonic acid (PFOS), similar to perfluorooctanoic acid (PFOA), is a synthetic chemical that has been classified as a persistent organic pollutant (POP) by the Stockholm Convention since 2009. Due to the wide previous usage, high stability, high bio-accumulative, and low degradative properties is the reason that PFOS has been found in several compartments of the environment including ocean water, ground water, air, and sediments. Due to the strong interactions generated by the sulfonic acid end, this compound has a tendency to stay in the environment for long periods of time and has proved to be difficult in the removal from …

An Innovative Triboelectric Stent Sensor: Prospective Cardiovascular Health Monitor Device, Ulises Vidaurri Romero

Theses and Dissertations

Previous research that has focused on TENGs have lacked the proper application of this energy generator. Currently, heart disease remains the leading cause of death in the United States. With increasing demand for self-sustainable medical devices, this nitinol health monitor sensor device (NHMS) integrates the TENG applications with medical applications. The NHMS features memory shape nitinol electrodes that preserves the device structure while using PDMS and PVDF triboelectric effect to measure heart rate, blood pressure, and breathing patterns. Three constant pressures were measured in this study. At a constant pressure of stage 1, the NHMS produces an average AC of …

Evaluating The Biological Activities Of Novel Histone Deacetylase Inhibitors (Hdaci) In Adherent And Nonadherent Tumor Cell Lines, Samer Alanani

Theses and Dissertations

Epigenetic dysregulations are linked to many human diseases including neurodegenerative disorders, immunodeficiencies, cardiac disease, and most notably cancer. Changes in the mechanisms of histone modifications have been recognized as hallmarks of carcinogenesis. One of these modifications is histone acetylation which is regulated by the activities of histone acetyltransferases (HATs) and histone deacetylases (HDACs). The reversible actions of these enzymes govern the acetylome and maintain its balance allowing for activation and repression of gene transcription. However, aberrant overexpression of HDACs in certain tumors is associated with decreased levels of transcription leading to tumor progression and survival. Hence, small-molecule histone deacetylase inhibitors …

Electrospun Pcl And Pcl/Gel Microfiber Scaffolds As Prototypes For Anterior Cruciate Ligament (Acl) Regeneration And Repair, Diego Rivera

Theses and Dissertations

Polycaprolactone (PCL) is a polymer that has been a focus of tissue engineering due to its range of applicability for biomedical applications. Synthesis of PCL from a microwave-assisted and stannous octoate-catalyzed ring-opening reaction with ε-caprolactone was accomplished. Aligned-fiber microfiber mats were generated via electrospinning for characterization. PCL microfiber mats were characterized via FTIR and scanning electron microscopy. These PCL microfiber mats were mechanically tested to examine their applicability as tools for knee ligament repair. During tensile testing, non-fiber aligned mats lacked the sufficient elastic modulus. Fiber-aligned PCL samples both and gelatin-coated were tested and showed enhanced elastic modulus and extension …

Microwave Assisted Depolymerization Of Waste Pet Bottles Via Glycolysis, Kingsley Bassey

Theses and Dissertations

One of the most promising and sustainable chemical depolymerization methods for managing the complex environmental problem arising from waste poly(ethylene) terephthalate (PET) bottles is glycolysis. However key challenges such as longer reaction times, complex separation procedures for the depolymerized products, selectivity, thermally stable catalyst need to be addressed.

In this work, we investigated the glycolysis of waste PET under microwave conditions using 1,5,7-Triazabicyclo [4.4.0] dec5-ene (TBD) and 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU) as catalyst. We evaluated the effect of reaction parameters such as temperature, catalyst concentration and time on PET depolymerization rate (%PET conversion) and product yield. The reaction was conducted …

Microwave Spectroscopy Of Cyclohexanecarboxylic Acid, Chlorosulfonic Acid, And Its Interaction With Water, Diego Erik Rodriguez

Theses and Dissertations

This study combines computational chemistry and microwave spectroscopy to simulate the behavior of two molecules: cyclohexanecarboxylic acid and chlorosulfonic acid. In this thesis, cyclohexanecarboxylic acid will be observed on its own. On the other hand, chlorosulfonic acid will be observed on its own as well as its interaction with one, two, and three water molecules. Chapter 1: Introduction will provide insight on published literature related to cyclohexanecarboxylic acid, chlorosulfonic acid, and perfluoroalkyl substances. Chapter 2: Computational Chemistry will provide the reader with information about the foundation of computational chemistry including theory and development of the science. Chapter 3: Microwave Spectroscopy …

Total Synthesis Of E Stereoisomers Of Bilirubin Oxidation Products, Tess C. Ruiz

Theses and Dissertations

The purpose of the research was to synthesize the E stereoisomer of Bilirubin Oxidation Products that had not been synthesized through a total organic synthesis at the start of this project. There were numerous different procedures for the bromination of citraconic anhydride performed in an attempt to optimize yield and purity. A proposed scheme for the total synthesis of the E isomers was constantly updated and altered while the project was ongoing. The bioactivity of the compounds was to be tested if the project had been finished. This might have contributed to a greater understanding of their function and association …

Optimization And Application Of Electrochemical Probes For Neurotransmitter Detection, Colby E. Witt

Theses and Dissertations

The brain is a complex matrix that is difficult to study. Signaling molecules, neurotransmitters, are constantly being released and sequestered back into neurons within milliseconds to facilitate communication and normal function, a process called neurotransmission. There are few analytical techniques available to selectively probe such a dynamic system, and even fewer can detect these discrete changes in real-time. In order to make robust measurements in the brain you need speed, sensitivity, selectivity and small probe size, which are encompassed by fast-voltammetry with microelectrodes. Traditional fast-voltammetry at carbon fiber microelectrodes (fast-scan cyclic voltammetry (FSCV)) requires background subtraction to overcome the large …

Polymeric Sorbents For Solid-Phase Extraction (Spe) Of Polar Analytes And Carbon Dioxide Capture, Ishwor Karki

Theses and Dissertations

The main topics of this dissertation are: 1) the study of hydrophilic-lipophilic balance (HLB) polymer monoliths for solid-phase extraction (SPE) applications, 2) molecularly imprinted polymers (MIPs) for capturing the CO2 gas and 3) the application of symmetry-adapted perturbation theory (SAPT) calculations to examine the origins of non-covalent interactions.

HLB polymers are popular sorbent materials in separation science. The Divinylbenzene-co-N-vinylpyrrolidone (DVB-co-NVP) polymer is one of the most widely used general-purpose HLB polymers. Despite the popularity of HLB polymer stationary phases, the studies of the adsorption properties of DVB-co-NVP have only been reported over a narrow …

Teaching An Old Dog New Tricks: Synthesis And Applications Of Novel Polybenzimidazole (Pbi) Membranes, Laura Ann Murdock

Theses and Dissertations

Polybenzimidazoles (PBIs) represent a class of performance polymers that display exceptional thermal and oxidative stability. For almost thirty years, PBI membranes have been investigated as promising candidates for next-generation alternative energy devices, including high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) and vanadium redox flow batteries (VRBs). Issues with the production of PBI membranes arise from their inherent low solubility in organic solvents. Thus, conventional approaches typically yield membranes that have limited molecular weight and generate significant waste in preparation, due to the large quantity of solvent required to dissolve PBIs for membrane casting.

Presented herein is the development of …

From Persistent Radicals To Conductivity: A Structure Property Investigation In A Series Of Urea-Tethered Halogenated Triphenylamines, Muhammad Saddam Hossain

Theses and Dissertations

Triphenylamines (TPAs) are known to form persistent organic radicals either by chemical, electrochemical or photoinduced oxidation. Typically, fully para-substituted TPAs form stable radical cations while the radical cations in partially substituted systems quickly degrade. Herein, we study the effects of solid-state organization on a series of urea tethered halogenated TPAs 1 (X = H, Cl, Br, I) and compare their radical cation formation and persistence after UV-irradiation. These halogenated urea tethered TPAs were examined by single-crystal X-ray diffraction where their assembly was guided by threecentered urea hydrogen bonding interaction. As expected, all compounds form photogenerated radical cations in solution, but …

Investigations On The Surface Chemistry Of Colloidal Quantum Dots Towards Fluorescent Biological Probes, John Hardin Dunlap

Theses and Dissertations

Colloidal semiconductor quantum dots (QDs) have garnered significant interest as promising materials for biological applications due to their improved photostability and narrow, tunable photoluminescence properties compared to organic fluorophores. To facilitate their utility as fluorescent bioimaging probes, QDs must undergo post-synthetic modifications to exchange their native hydrophobic ligands from synthesis with hydrophilic ones that enable colloidal dispersions in aqueous environments. Many examples exist that demonstrate surface modifications for water-soluble QDs and their efficacy in biological systems, however, there is a need to develop a more thorough understanding of how hydrophilic ligands coordinate to QD surfaces in order to develop more …

Enhancing Charge Carrier Mobility In Colloidal Quantum Dots For Technological Applications, Fiaz Ahmed

Theses and Dissertations

Colloidal quantum dots (QD) are promising semiconducting materials to engineer photovoltaic and optoelectronic devices due to tunable size-dependent absorption and emission properties. These materials are important as they don’t need complicated equipment and huge setup investment for industrial applications. If formulated into a kind of stable nano-ink, these QDs can be incorporated into devices using the most economical processing technologies, spray or roll to roll printing. More importantly, these are compatible with thin-film stacked devices and circuitry that can be formed on heat-sensitive and flexible substrates to make flexible wearable devices and sensors that are difficult to achieve with crystalline-based …

Characterization Of A Novel Fe-S Cluster Transfer Pathway Between Grx4 And Sufa In Escherichia Coli, Enis Sanchez

Theses and Dissertations

Biogenesis of iron-sulfur (Fe-S) clusters is an essential process in living organisms due to the critical role of Fe-S cluster proteins in a myriad of cellular functions. During the assembly of Fe-S clusters, multi-protein complexes are used to drive the mobilization and protection of reactive sulfur and iron intermediates, regulate assembly of various Fe-S clusters on an ATPase-dependent, multi-protein scaffold, and target nascent clusters to their downstream protein targets. In each of the Fe-S cluster biogenesis steps, specific protein-protein interactions (PPIs) are required for proper function of the assembly pathway. The target pathway is the sulfur formation (Suf) pathway for …

Investigating The Chemistry Of Harmful Algal Blooms And Microbial Communities In The Natural Environment, Samuel Patrick Putnam

Theses and Dissertations

Cyanobacteria has existed on the planet for over 3 billion years, and as technology, science, and industry have allowed us to shape our world, these changes have caused a proliferation of biomass. Higher carbon dioxide levels in the atmosphere, warmer temperatures, and rapid increases in the nutrient cycle have created excellent growing conditions for cyanobacteria, making them endemic in fresh waters throughout the world. The work in this dissertation was directed towards the secondary metabolites produced by cyanobacteria and other surrounding microbes and understanding their concentrations and release in natural systems. Analytical methods were developed for the extraction and quantification …

Investigating Provenance And Authenticity Using Icp-Ms In The University Of Wisconsin-Milwaukee Art Collection: A Case Study Of Luristan Bronzes, Hannah Rillie

Theses and Dissertations

The University of Wisconsin-Milwaukee Art Collection (UWMAC) holds a group of supposed Luristan bronzes with limited provenances. The lack of provenance, archaeological or otherwise, coupled with the prevalence of forged Luristan bronzes across private and public collections introduced questions of authenticity regarding the UWMAC’s collection of bronzes. To address these questions, the typical art historical and visual analyses were conducted to supplement the chemical compositional analysis done using inductively-coupled plasma mass spectrometry. Of the three artifacts successfully sampled and tested, the Ibex Whetstone Handle (1985.002.38) was determined to be iron while the Master of Animals Finial for Standard (1985.002.48) and …

Applications Of Vanadium Phthalocyanine In Catalytic, Acid-Based Medium To Couple Sugar Molecules, Juan Ricardo Luna

Theses and Dissertations

The vanadium-substituted tetraazatetrabenzoporphyrin, vanadium phthalocyanine, was synthesized via reflux and characterized using FITR and XRD analysis. Subsequent to synthesis, the vanadium phthalocyanine was studied as a catalyst in redox reactions to convert fructose to different molecules, the products were predominately levulinic methyl ester and heptadionic acid. The ability to convert fructose to other compounds, such as alkyl levulinic derivative, is an important process to help eliminate reliance on traditional chemical feed stocks and promote alternative fuels. Levulinic acid has been commonly used as a starting material in the synthesis of biofuels and a precursor for pharmaceuticals, plasticizers, THF derivatives, γ-valerolatone. …

Nd Doped Zinc Oxide Based Flexible Pvdf Polymer Composite For Energy Harvesting And Sensory Application, Muhtasim Ul Karim Sadaf

Theses and Dissertations

Flexible Piezoelectric devices have garnered a lot of attention for their potential as energy harvesters and transducers. Zinc Oxide particularly has been doped with different metals and has been incorporated in functional polymers in order to produce flexible piezoelectric devices. In this work, a Neodymium doped Zinc Oxide based flexible piezoelectric energy harvester and sensory device has been developed. For that, neodymium doped zinc oxide has been synthesized using wet chemical co-precipitation method and then has been incorporated in Polyvinylidene Difluoride (PVDF) polymer matrix along with Multiwalled Carbon Nanotubes (MWCNT) to produce flexible piezoelectric films. Silver paste was applied on …