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Glutamic Acid Resorcinarene-Based Molecules And Their Application In Developing New Stationary Phases In Ion Chromatography, Tayyebeh Panahi

Theses and Dissertations

Resorcinarenes can be functionalized at their upper and lower rims. In this work, the upper rim of a resorcinarene was functionalized with glutamic acids and the lower rim was functionalized with either methyl or undecyl alkyl groups. The cavitands were characterized by nuclear magnetic resonance (NMR), mass spectrometry (MS), UV-vis spectroscopy, dynamic light scattering (DLS) and electron microscopy. The binding of resorcinarene with amine guests was studied in DMSO by UV-vis titration. The obtained binding constants (K values) were in the range of 12,000-136000 M-1. The resorcinarenes were shown to form aggregates in a variety of solvents. The aggregates were …

Analyses Of Mrna Cleavage By Rele And The Role Of Trna Methyltransferase Trmd Using Bacterial Ribosome Profiling, Jae Yeon Hwang

Theses and Dissertations

Protein synthesis is a fundamental and ultimate process in living cells. Cells possess sophisticated machineries and continuously carry out complex processes. Monitoring protein synthesis in living cells not only inform us about the mechanism of translation but also deepen our insights about all aspects of life. Understanding the structure and mechanism of the ribosome and its associated factors helped us enlarge our knowledge on protein synthesis. Recently, with the dramatic advances of high-throughput sequencing and bioinformatics, a new technique called ribosome profiling emerged. By retrieving mRNA fragments protected by translating ribosomes, ribosome profiling reveals global ribosome occupancy along mRNAs in …

Inhibitory Effects Of Unique Sulfonamides On Leishmania Tarentolae And Potential Pathway Of Inhibition, Jade M. Katinas

Theses and Dissertations

Leishmaniasis is an endemic disease caused by the protozoan parasite Leishmania. Current treatments for the parasite are limited by cost, availability, and drug resistance as the worldwide occurrence of leishmaniasis continues to be more prevalent. Sulfonamides are a class of compounds with medicinal properties that have been used to treat bacterial and parasitic diseases via various pathways. In this study, newly synthesized, unique structural analogs of sulfonamide compounds were assessed for their impact on Leishmania cell viability and potential pathways for inhibition were evaluated. Leishmania tarentolae (ATCC Strain 30143) axenic promastigote cells were grown in BHI medium and treated with …

Synthesis And Performance Analysis Of Polyurethane Foam Nanocomposite For Arsenic Removal From Drinking Water, Faten Bakri Hussein

Theses and Dissertations

Water contamination by various heavy metal pollutants such as, Lead, Arsenic, Cadmium, and Mercury, have severe toxic effects on living organisms and humans. High concentrations of arsenic in drinking water cause serious damage to the central and peripheral nervous systems, as well as, the dermal, cardiovascular, gastrointestinal, and respiratory systems. Arsenic contamination of ground water poses a substantial concern in many countries throughout the world, including the United States.

Considerable research work, aimed at finding and developing various separation and treatment techniques, has been conducted over the past few decades. The conventional treatment methods of arsenic involve coagulation with ferric …

Variable Pathlength Cavity Spectroscopy Development Of An Automated Prototype, Ryan Schmeling

Theses and Dissertations

ABSTRACT

VARIABLE PATHLENGTH CAVITY SPECTROSCOPY

DEVELOPMENT OF AN AUTOMATED PROTOTYPE

by

Ryan Andrew Schmeling

The University of Wisconsin-Milwaukee, 2016

Under the Supervision of Professor Joseph H. Aldstadt III

Spectroscopy is the study of the interaction of electromagnetic radiation (EMR) with matter to probe the chemical and physical properties of atoms and molecules. The primary types of analytical spectroscopy are absorption, emission, and scattering methods. Absorption spectroscopy can quantitatively determine the chemical concentration of a given species in a sample by the relationship described by Beer’s Law. Upon inspection of Beer’s Law, it becomes apparent that for a given analyte concentration, …

Encapsulation Of Cationic Fluorescent Dyes And Photosensitizers Into The Nanoscopic Domains Of Poly(Ethylene Glycol)-B-Poly(Ε-Caprolactone) Micelles, Zhe Cao

Theses and Dissertations

This study describes an initial systematic investigation on the molecular determinants associated with the effective encapsulation (or lack thereof) of small cationic molecules into the nanoscopic domains of Poly(ethylene glycol)-b-poly(ε-caprolactone) micelles. Out of the seven model dyes investigated here (methylene blue, crystal violet, rhodamine 123, styryl 9M, HITC, DIR and Cardiogreen) only DiR and Cardiogreen were found to partition into the core region of the respective polymeric micelles with a high degree of efficiency. Evidences of weak interactions between styryl 9M and HITC with the corona region of these micelles were also found. No experimental evidences indicating any significant interaction …

Role For Reactive Oxygen Species In Methamphetamine Modulation Of Dopamine Release In The Striatum, David Matthew Hedges

Theses and Dissertations

Methamphetamine (METH) is a highly addictive substance that is highly prevalent in today’s society, with over 1 in 20 adults over 26 having taken it at least once. While it is known that METH, a common psychostimulant, acts on both the mesolimbic dopamine (DA) and nigrostriatal DA systems by affecting proteins involved in DA reuptake and vesicular packaging, the specific mechanism of what is known as METH neurotoxicity remains obscure, but has been shown to involve oxidative stress. Studies have shown that reactive oxygen species act on the same proteins that METH affects. Oxidative species have also been known to …

Placental ‘€˜Omics’€™ Study To Understand The Pathogenesis Of Preeclampsia, Komal Kedia

Theses and Dissertations

Preeclampsia (PE) is a potentially fatal complication of pregnancy characterized by an increase in blood pressure (>140/90 mmHg) and proteinuria (>300 mg/24 hrs), often accompanied by edema. Symptoms of PE start after 20 weeks of gestation. If PE remains untreated, it can lead to eclampsia, grand-mal seizures responsible for most fatalities. PE is believed to affect 2-10% of pregnancies worldwide, and claims the lives of over 75,000 mothers and 500,000 newborns yearly. No therapeutic agents have been developed to prevent or cure PE. Part of the reason for this is the absence of a complete understanding of the …

Development Of Arginyl-Trna Synthetase From Pseudomonas Aeruginosa As A Platform To Screen For Inhibitors Of Protein Synthesis, Daniel Cantu

Theses and Dissertations

Pseudomonas aeruginosa is a Gram- negative bacteria that is the leading cause of mortality in immunocompromised patients. Arginyl-tRNA synthetase (ArgRS) is an enzyme that catalyzes the covalent attachment of arginine to the cognate tRNAArg during protein synthesis. Scintillation proximity assays (SPA) were adapted to the aminoacylation assay and used to screen, one natural compound library (800) and one synthetic compound library (890) to identify inhibitors of the activity of ArgRS. Five compounds were identified which inhibited greater than 50% of enzymatic activity, two of these compounds (BT04F10 and BT11F03) exhibited promising MICs against Gram+ bacteria and moderate activity against Gram- …

Identification Of Synthetic Chemical Compound Inhibitors Of Pseudomonas Aeruginosa Protein Synthesis And The Development Of Lead Series, Stephanie O. Palmer

Theses and Dissertations

Pseudomonas aeruginosa is a ubiquitous Gram-negative bacteria and a primary cause of nosocomial infections. An aminoacylation/translation (A/T) assay was developed using P. aeruginosa components to perform poly(U) mRNA directed protein synthesis. Using scintillation proximity assay (SPA) technology a high-throughput screening (HTS) platform was developed. A synthetic chemical compound library (>900) was screened, 36 hit compounds were identified and molecular targets were determined. Compounds were analyzed for enzymatic inhibition (IC50) and inhibition of bacterial cultures (MIC). Time-kill studies determined bacterial growth to be bacteriostatic or bactericidal in the presence of inhibitor. Mechanism of action, effects on eukaryotic cytosolic and mitochondrial …

Hydrodesulfurization Of Dibenzothiophene Using Comos2, Jacob S. Sollner

Theses and Dissertations

The hydrodesulphurization (HDS) of crude oils is an important industrial process to remove sulfur from fuels. In this study, DBT was used as a model compound to study the removal of sulfur from a decahydronaphthalene solution. The catalyst was synthesized through low pressure pathways in the absence of H2S. All the synthesized catalyst were investigated using a combination of SEM, RAMAN spectroscopy, and XRD. The materials were studied for their ability to remove DBT from solution and the reaction products were analyzed. It was observed that the major reaction pathway was the direct desulphurization pathway and zero order reaction kinetics …

Molecular Dynamic Simulation Studies Of The Androgen Receptor Complexed With 5Α-Dihydrotestosterone And An Allosteric Ligand, Everardo Villarreal Ii

Theses and Dissertations

Receptors are important drug targets for the pharmaceutical industry, since they are involved in many illnesses. Nuclear receptors are a subset of receptors that control a variety of physiological events, by expression of genes from DNA. One of the nuclear receptors, the androgen receptor, is a steroid binding receptor that controls a variety of regulatory and development functions in the body. It is also the cause of some types of cancer, so the inhibition of this receptor is crucial. One of the processes studied to inhibit the function of the receptor is to see if an allosteric ligand, TRIAC, can …

Removal Of Perfluorooctanoic Acid From Water Using Primitive, Conventional And Novel Carbonaceous Sorbent Materials, Christopher K. Brown

Theses and Dissertations

Polyfluoroalkyl Substances (PFAS), like perfluorooctanoic acid, have been used for the last 50 years in a wide variety of industrial processes and consumer-based products, including polymer additives, lubricants, fire retardants and suppressants, pesticides, and surfactants (Buck et al. 2015). The Department of Defense (DoD) has used PFAS-based Aqueous Film Forming Foam (AFFF) at fire training facilities and aircraft hangars. AFFF has contaminated approximately 600 sites classified as fire training facilities with PFAS (Huang, 2013).

This study focused on testing the most likely carbonaceous adsorbent compounds to remediate PFAS-contaminated sites on Air Force installations. Batch tests were performed to determine the …

Discovery Of Low-Molecular Weight Novel Serum Biomarkers For Diagnosing Preeclampsia And Alzheimer's Disease, Swati Anand

Theses and Dissertations

Preeclampsia (PE), a life threatening pregnancy-related disorder, is characterized mainly by new onset of hypertension and proteinuria after 20 weeks of gestation. Currently, PE cannot be predicted prior to onset of symptoms and there is no cure for the disease. There is a clear value in having biomarkers able, early in a pregnancy, to identify women at risk for PE so that proper treatment therapies could be developed. Although a number of serum candidate markers have been proposed to be altered in PE patients, their use is limited due to poor sensitivity and specificity. Therefore, there is ongoing need for …

Novel Sputtered Stationary Phases For Solid Phase Microextraction, And Other Coatings And Materials For Surface Applications, Anubhav Diwan

Theses and Dissertations

The primary focus of my work has been to prepare new solid adsorbents for solid phase microextraction (SPME) via sputtering of silicon. The orientation of the silica substrates/fibers and the sputtering pressure induced the formation of porous and columnar structures. Sputtering was performed for different times to yield fibers with different thicknesses. Piranha treatment of the surface increased the concentration of silanol groups, which underwent condensation with vapor deposited octadecyldimethylmonomethoxy silane to incorporate octadecyl chains onto the fiber surfaces. Silanized, sputtered fibers were preconditioned for 3 h at 320 °C to remove the unreacted chains. Comparison of the extraction efficiencies …

Development And Application Of New Solid-State Models For Low-Energy Vibrations, Lattice Defects, Entropies Of Mixing, And Magnetic Properties, Jacob M. Schliesser

Theses and Dissertations

Low-temperature heat capacity data contain information on the physical properties of materials, and new models continue to be developed to aid in the analysis and interpretation of heat capacity data into physically meaningful properties. This work presents the development of two such models and their application to real material systems. Equations describing low-energy vibrational modes with a gap in the density of states (DOS) have been derived and tested on several material systems with known gaps in the DOS, and the origins of such gaps in the DOS are presented. Lattice vacancies have been shown to produce a two-level system …

14-3-3Ζ Regulation Of Metastasis Through Mediation Of Liprin-Α And Liprin-Β, Rachel Hynes

Theses and Dissertations

Cancer is a set of varied and diverse diseases that share common characteristics, such as active proliferation, increased replicative potential, and tissue invasion or metastasis. One protein, 14-3-3ζ, is shown to be upregulated in a number of different cancers and also correlates with poor patient prognosis, recurrence, and mortality. This protein comes from a family of adapter proteins known for their scaffolding ability, pro- and anti-oncogenic capabilities, and affinity for phosphorylated substrates. It has been shown previously to participate in cancer progression, subversion of apoptosis, and to increase chemoresistance. Herein we will discuss the ability of 14-3-3ζ to promote distant-site …

Solid State Synthesis And Characterization Of The Rare Earth-Free Anti-Perovskites Sr2.5-Xba0.5 Al1-Xp Xo4 F ( 0 ≤ X ≤ 0.15 ), Sr3al1-Xy Xo 4 F ( 0 ≤ X ≤ 1 ), And Sr2.5-X/2ba0.5 Al1-Xhfxo4 F ( 0 ≤ X ≤ 0.1 ) As Potential Phosphor Materials, Sean Thomas Keil

Theses and Dissertations

Typical lighting systems such as incandescent and fluorescent bulbs are common in homes but are rather inefficient compared to the newer light emitting diodes (LEDs). LED-based lamps can be constructed to generate white light by combining a red, green, and blue LED, or by using an LED light source (typically with a low wavelength) with a complimentary phosphor coating to produce white light. The latter, known as phosphor-conversion (PC) LEDs, is the primary focus of this research, looking specifically at rare earth-free options for these phosphor coatings.

Anti-perovskites are a potential lattice type for this type of conversion, in particular …

Determination Of Fine Particulate Matter Composition And Development Of The Organic Aerosol Monitor, Paul Michael Cropper

Theses and Dissertations

Tropospheric fine particulate matter (PM) poses serious health risks and has a significant impact on global climate change. The measurement of various aspects of PM is challenging due to its complex chemical nature. This dissertation addresses various aspects of PM, including composition, measurement, and visibility. The U.S. Environmental Protection Agency (EPA) proposed a new secondary standard based on visibility in urban areas using 24-h averaged measurements of either light scatter or PM concentration. However shorter averaging times may better represent human perception of visibility. Data from two studies conducted in Lindon, UT, 2012, and Rubidoux, CA, 2003, were used to …

The Dawn Of New Quantum Dots: Synthesis And Characterization Of Ge1-Xsnx Nanocrystals For Tunable Bandgaps., Richard J. Esteves

Theses and Dissertations

Ge_1-xSn_x alloys are among a small class of benign semiconductors with composition tunable bandgaps in the near-infrared spectrum. As the amount of Sn is increased the band energy decreases and a transition from indirect to direct band structure occurs. Hence, they are prime candidates for fabrication of Si-compatible electronic and photonic devices, field effect transistors, and novel charge storage device applications. Success has been achieved with the growth of Ge_1-xSn_x thin film alloys with Sn compositions up to 34%. However, the synthesis of nanocrystalline alloys has proven difficult due to larger discrepancies (~14%) in …

The Development Of Bicyclic Peptide Library Scaffolds And The Discovery Of Biostable Ligands Using Mrna Display, David E. Hacker

Theses and Dissertations

Peptides are a promising class of therapeutic candidates due to their high specificity and affinity for cellular protein targets. However, peptides are susceptible to protease degradation and are typically not cell-permeable. In efforts to design more effective peptide drug discovery systems, investigators have discovered that incorporation of non-canonical amino acids (ncAAs) and macrocyclization overcome these limitations, making peptides more drug-like.

In this work, we exploit the promiscuity of wild-type aminoacyl-tRNA synthetases (aaRSs) to ‘mischarge’ ncAAs onto tRNA and ribosomally incorporate them into peptides using a cell-free translation system. We have demonstrated the ability to incorporate five ncAAs into a single …

Physical Property Control In Core/Shell Inorganic Nanostructures For Fluorescence And Magnetic Targeting Applications, Stephen K. Roberts

Theses and Dissertations

Nanomaterials show immense promise for the future in numerous areas of application. Properties that are unique from the bulk material and are tunable allow for innovation in material design. This thesis will focus on controlling the physical properties of core/shell nanostructures to enhance the utility of the materials.

The first focus is on the impact of different solvent mixtures during the shell growth phase of SILAR based core/shell quantum dot synthesis is studied. Gaining insight into the mechanism for SILAR growth of core/shell nanoparticles allows improved synthetic yields and precursor binding, providing enhanced control to synthesis of core/shell nanoparticles. The …

Investigating The Effects Of Glutathione And Other Key Proteins On Iron Homeostasis And Subcellular Redox Balance In Yeast Model Systems, Kirsten Renee Collins

Theses and Dissertations

Iron homeostasis in Saccharomyces cerevisiae is controlled through several pathways and is important because too much iron can cause cellular damage. Iron homeostasis in yeast is primarily controlled by transcription factors Aft1 and Aft2 which bind to the iron regulon to induce iron uptake when iron levels are low. When iron levels are sufficient, Aft1 and Aft2 are bound and inhibited by monothiol glutaredoxins (Grxs) Grx3 and Grx4. These Grxs are also involved in iron trafficking in the cell and bind to and deliver iron-sulfur clusters to multiple proteins.

The first part of this thesis focuses on determining if excess …

Forensic Characterization Of Dyes From Synthetic Textile Fibers Exposed To Outdoor And Laundering Effects By Ultra Performance Liquid Chromatography And Spectral Analysis, Molly Rebecca Burnip

Theses and Dissertations

Textile fibers found in an investigation are trace evidence that can connect a suspect to a victim or crime scene. Examination involves comparison of the color and morphology of a questioned fiber to a known fiber with optical spectroscopy. Fibers are considered class evidence, so evaluating more characteristics increases their significance as evidence if a match cannot be excluded. Acrylic, nylon, and polyester are textile polymers that require different extraction solvents based on the polymer chemistry. Methods have been developed for UPLC analysis of basic dyes on acrylic, acid on nylon, and disperse dyes on polyester. After microextraction from single …

From Model Systems To Real Catalysts: Bridging The Pressure And Materials Gaps, Audrey S. Duke

Theses and Dissertations

For decades a fundamental understanding of heterogeneous catalysts has been pursued for rational catalyst design using model systems under ultrahigh vacuum (UHV) conditions; however, there exist stark differences between the simplified models investigated under UHV and the industrial catalysts used at high pressures. To bridge these gaps, it becomes essential to utilize progressively more complex materials and to correlate their surface structure and activity using incrementally higher pressure techniques. In this work, both model Pt-Re catalysts and powdered metal-organic frameworks (MOFs) were studied using a suite of traditional UHV surface science techniques in addition to ambient pressure X-ray photoelectron spectroscopy …

Cdk8 And Cdk19 As Novel Regulators Of Bmp4 Induced Emt In Cancer, Anne Elizabeth Serrao

Theses and Dissertations

Bone morphogenetic protein 2/4 (BMP2/4), members of the transforming growth factor β (Tgf-β) superfamily, play a dichotomous role in the progression of cancers through cell growth suppression and the enhancement of tumorigenesis in a variety of cancers. Cyclin dependent kinase 8 (CDK8), a protein kinase that regulates gene transcription, is involved in a variety of cancers including breast and pancreatic cancers as well as in mediating BMP2 signaling via its canonical Smad1 pathway. Our studies show that BMP4 induced EMT signals primarily though Smad1 and that Yap1, a transcriptional co-activator, is necessary for BMP4 induced EMT. Using a highly specific …

Virus Particles Provide Nanotopographical Cues For Osteogenic Differentiation Of Mesenchymal Stem Cells, Kamolrat Metavarayuth

Theses and Dissertations

One key aspect of tissue engineering is to develop biomimetic scaffolding materials that can modulate the proliferation, self-renewal and differentiation of multipotent stem cells into different lineages. Bone marrow derived mesenchymal stem cells (BMSCs) can differentiate into several target cells such as osteoblasts, chondrocytes, adipocytes, and smooth muscle cells. BMSCs are commonly used for in vitro osteogenesis studies in bone tissue engineering field. However the mechanisms and signaling pathways that these cells use to recognize and response to biomaterial surface are still unclear. This dissertation focuses on investigating the effect of chemical and physical cues introduced by virus nanoparticles on …

Using Synthetic Lectins To Investigate Metastatic Potential In Colon Cancer, Erin E. Gatrone

Theses and Dissertations

Cancer is a disease that affects millions of people each year and it is well established that early diagnosis is a key factor towards improving survival rate, with that in mind there is a great need for better diagnostics. From the earliest onset of cancer, changes can be detected in the type and amount of carbohydrates expressed by the cancer cells, i.e., aberrant glycosylation. This process results in differing glycosylation patterns that can be used to detect cancer. Aberrant glycosylation can also greatly affect the potential of cancer cells to metastasize and can be used to stage the disease as …

Synthesis And Utility Of Bis-Urea Macrocycles As Nanoreactors And As Ligands For Metal Organic Materials, Sahan R. Salpage

Theses and Dissertations

“Supramolecular chemistry” powered by non-covalent interactive forces forms the crux in the area of host-guest chemistry. Supramolecular assemblies often have different chemical and physical properties than that of its individual molecular entities and are used to develop novel functional materials. Our expertise involves making functional materials from macrocycles, which contain two urea groups and two rigid C shaped spacer groups. These individual macrocyclic components can self-assemble through hydrogen bonding and other non-covalent interactions to form porous supramolecular assemblies that can be used as confined reaction environments and as ligands to synthesize novel metal organic materials.

This dissertation focuses on studying …

Investigating Structure-Activity Relationships Of Sl11 To Develop A Better Prostate Cancer Diagnostic, Rong Huang

Theses and Dissertations

Prostate cancer is now the second leading cause of cancer death in American men. Since many of the diagnostics either have high false results or risky, it’s important to have better diagnostics and earlier diagnosis of prostate cancer. Aberrant glycosylation is a hallmark of cancer. When cancer occurs, aberrant glycosylation occurs, therefore, glycosylation patterns may provide information about different cancer types and metastatic potential. In order to study and use these glycosylation patterns, the boronic acid functionalized synthetic lectins that can interact with glycans have been developed. The work described here focuses on 1) the structure activities of synthetic lectins …