Chemistry Commons^™

Metal-Organic Frameworks And Mof-Derived Carbon Materials For Fuel Cell Applications, Kia Williams

USF Tampa Graduate Theses and Dissertations

Rapid industrial globalization and technological development and energy consumption across the globe has significantly increased in response to mounting energy needs. The necessity for alternative and sustainable energy conversion devices has become apparent with the growth of energy utilization. In recent years, many research efforts have been made in the development of low-cost, efficient, environmentally friendly energy conversion devices. One type of energy conversion device, polymer electrolyte membrane fuel cells (PEMFCs), uses hydrogen oxidation at the anode and oxygen reduction at the cathode, with a solid-state proton conducting membrane between to generate energy with water as a by-product. PEMFCs use …

Design And Synthesis Of Cpg-Lytic Peptide Conjugate, Brachytherapy Beads And A Combinatorial Library Of Primary Amines Used As Potential Therapeutics In The Treatment Of Cancers, Josanne-Dee Woodroffe

USF Tampa Graduate Theses and Dissertations

Cancer remains one of the most feared diseases affecting the modern world. Second to heart disease, it is the largest cause of deaths, affecting one in three persons. Cancer cells are formed when normal, healthy cells become damage, losing their normal regulatory mechanism that control cell growth. There are many different types and progression of these cancer cells that determine the type of treatment a patient receives. The primary focus of this dissertation is to propose three studies of anticancer agents. In Chapter one, a CpG-lytic peptide conjugate was designed to target receptors on the cell membrane to concentrate the …

Expression, Purification And Characterization Of Egf27 From The Notch1 Abruptex Region, Huimin Zhong

LSU Master's Theses

Notch proteins are transmembrane proteins and act as receptors in Notch signaling, which is related to diverse developmental diseases including cancer.^1-2 The mouse Notch1 protein contains 36 tandem epidermal growth factor-like (EGF) repeats in the extracellular domain (ECD).^1-2 Our research project focused on the structural study of the Abruptex region consisting of EGF24-29 in the ECD. The fact that this region is a potential competitor to a Notch ligand, because of its high glycosylation and flexibility, makes it important to solve the three-dimensional structure and investigate the glycosylation effect on the structure of the Abruptex region.³ By …

Hydrogeochemical Investigation Of Recharge Pathways To Intermediate And Regional Groundwater In Cañon De Valle And Technical Area 16, Los Alamos National Laboratory, Brendan W. Brady

Civil Engineering ETDs

In aquifers consisting of fractured or porous igneous rocks, as well as conglomerate and sandstone products of volcanic formations, silicate minerals actively dissolve and precipitate (Eby, 2004; Eriksson, 1985; Drever, 1982). Dissolution of hydrated volcanic glass is also known to influence the character of groundwater to which it is exposed (White et al., 1980). Hydrochemical evolution, within saturated zones of volcanic formations, is modeled here as a means to resolve the sources feeding a perched groundwater zone. By observation of solute mass balances in groundwater, together with rock chemistry, this study characterizes the chemical weathering processes active along recharge pathways …

Investigating Scalable Manufacturing Of High-Conductivity Wires And Coatings From Ultra-Long Carbon Nanotubes, Pouria Khanbolouki

Mechanical Engineering ETDs

Carbon nanotubes (CNTs) are a promising candidate for next generation of electrical wirings and electromagnetic interference (EMI) shielding materials due to their exceptional mechanical and electrical properties. Wires and coatings from ultralong nanotubes that are highly crystalline, well-aligned and densely packed can achieve this goal. High-performance CNT conductors will be relatively lightweight and resistant to harsh conditions and therefore can potentially replace current conductors in many industries including aerospace, automotive, gas and oil.

This thesis investigates a new manufacturing approach, based on conventional solution coating and wire drawing methods, to fabricate high conductivity wires and coatings from ultra-long carbon nanotubes. …

Development Of Remote Hydroxylation Via Redox Catalysis And Mild Activation Of Thioglycosides For O-Glycosylation, Kristina Deveaux

LSU Doctoral Dissertations

The focus of this dissertation is the development of a C-H functionalization method using redox catalysis and the synthesis of saccharides using thioglycosides. Chapter 1 is a review of C-H functionalization and visible-light photoredox catalysis. Over the years there have been many significant contributions to the field of C-H functionalization. Select examples have been discussed and a foundation for the method developed in chapter 2 has been outlined. Chapter 2 discusses the development and optimization of a C-H functionalization method. This approach uses the Tz^o directing group and Ir(ppy)₃ to activate a remote C-H bond via 1,6- and …

Sol-Gel Niobia-Based Sorbents For The Enrichment Of Organophosphorus Compounds By Capillary Microextraction Online Coupled To High Performance Liquid Chromatography, Sheshanka Kesani

USF Tampa Graduate Theses and Dissertations

Sample preparation is a key step in chemical analysis, and includes isolation of target analytes, removal of interferences, preconcentration, and/or modification of target analytes (if needed). Sample preparation is also the most time-consuming and error-prone step in the whole analytical process. Traditional sample preparation techniques involve hazardous solvents. Considering the environmental and health safety, it is desirable to reduce or eliminate organic solvents in sample preparation. Solid phase microextraction (SPME) was introduced as a solvent free sample preparation technique. Capillary microextraction (CME) is one of the formats of SPME that can be easily coupled to high performance liquid chromatography (HPLC). …

Evaluation Of The Potential Hmga1-Ef24 Nexus In Human Colon Cancer, Madeline Diaz, Takita Sumter

The Winthrop McNair Research Bulletin

The architectural chromatin binding proteins High Mobility Group A1 (HMGA1) are proteins expressed at high levels in malignant cancers and induce neoplastic transformation. The protein is increased as the last step of the Wnt/B-catenin/TCF-4 pathway and mediates drug resistance, therefore correlating with a poor patient prognosis. HMGA1-mediated chemoresistance results from a self-protective process called cellular senescence. Analogs of the antioxidant, curcumin, when used in combination with traditional chemotherapeutic agents, are useful treatment options for drug resistant tumors. This study had two specific aims. The first being to investigate how colon cancer cells HCT116 respond to treatment with EF24. …

Formation Of Highly Functionalized Indole Through Carbon-Carbon Bond Cleavage, Ryan A. S. Pike

Chemistry and Chemical Biology ETDs

Indoles are one of the most abundant heterocycles found in nature and have a wide range of functions. There are a wide variety of indole synthesis methods known both in synthetic chemistry and through biosynthesis. Many of the known indole synthesis routes use a benzene derivative or cyclized ring structure derivative as a starting material. Here, we describe a novel synthetic method utilizing 1, 3-diketones and fumaronitrile with a catalytic amount of base to form a highly functionalized indole as our product. We have isolated and characterized 12 functionalized indoles.

Studies Of Polyacrylate Based Nanoparticle Emulsions, Faeez Mahzamani

USF Tampa Graduate Theses and Dissertations

Self-stabilizing polyacrylate nanoparticle emulsions were previously investigated in the Turos laboratory, and provided a new model for delivering antibiotics via encapsulation or covalent binding of the desired bioactive compound within the polymer nanoparticles. The method used the in water, free radical emulsion polymerization of butyl acrylate/styrene mixture to form the polymer chain stabilized with a surfactant. Current research in this dissertation further explores the versatility of related nanoparticle emulsion systems. Chapter 2 provides an overview of the loading of certain therapeutic drugs, such as 5-aminosalicylic acid and derivatives thereof, for the treatment of irritable bowel syndrome. Chapter 3 explores homo-polymer …

Construction Of Synthetic Signal Pathways In Mammalian Cells Via Induced Protein Proximity, Guihua Zeng

Chemistry and Chemical Biology ETDs

Cell signaling translates extracellular signals into intracellular processes that carry out cellular functions. The introduction of artificial signaling networks using synthetic biology methods has facilitated the investigation of signaling mechanisms and the generation of novel cell functions. Several synthetic biology methods that are based on chemical controls have been developed to provide precise temporal regulation. In my dissertation, we constructed new synthetic biology engineering strategies to control tailored cellular events.

Described in Chapter 2, we developed a new chemical strategy to generate de novo signaling pathways that link a signaling molecule, H₂O₂, to different downstream cellular …

Nanopatterns Of Zinc Phthalocyanines, Gold Nanoparticles, And Porphyrins Prepared Using Particle Lithography: Characterization Of Patterning Steps With Scanning Probe Microscopy, Ashley Marie Taylor

LSU Doctoral Dissertations

The growth and self-assembly of molecules on surfaces can be directly visualized at the molecular level using studies which combine nanoscale lithography and high-resolution imaging. Nanopatterning provides a unique and practical approach for direct views of surface changes after the key chemical steps of nanopatterning, providing landmarks and baselines for measuring growth in vertical and lateral dimensions. Controlling the arrangement of materials on surfaces at the nanoscale can be achieved using particle lithography. Arrays of well-defined nanostructures can be prepared with reproducible geometries and arrangement. Results for the preparation of nanopatterns produced with particle lithography are presented using high resolution …

Interactions Between Amyloid-Beta And Microglial Cells, Lisa Gouwens

Dissertations

Alzheimer’s disease (AD), the most common cause of dementia, is a neurodegenerative condition characterized by loss of memory and intellectual abilities. Intracellular plaques of aggregated amyloid-beta (Ab) protein are a well-known pathology associated with AD. Although symptoms usually appear late in life, the accumulation of Ab begins decades earlier and causes activation of microglia, the brain’s immune cells. The ensuing inflammation contributes significantly to neurodegeneration. Determination of the particular form of Ab that causes the most damage in the brain is one of the major questions in the AD field. My research focused on the interactions of microglia with monomers, …

Coupled Plasmon/Molecule Dynamics Near Core-Shell Nanoparticles: Synthesis, Ultrafast Characterization, And Quantum/Classical Modeling, Holden Tyler Smith

LSU Doctoral Dissertations

In this dissertation, the resonance coupling of chromaphoric dyes adsorbed on the surface of plasmonic nanoparticles (NPs) are investigated using a combined theoretical and experi- mental approach. Colloidal gold, gold-silver core-shell, silver-gold core-shell, and gold-silver- gold core-shell-shell NPs are considered. These NPs are thiolated with mercaptosuccinic acid, and malachite green dyes are adsorbed to the surface of the nanoparticle (NP) via elec- trostatic interactions. Second harmonic generation is used to determine the surface to the isotherm of the molecular dyes to the colloidal nanoparticle surface. Adsorption isotherms show that the SHG intensity increases as the concentration of dye increases, reaching …

Cytochrome C As A Peroxidase: Activation Of The Precatalytic Native State By H, Victor Yin, Gary S Shaw, Lars Konermann

Chemistry Publications

In addition to serving as respiratory electron shuttle, ferri-cytochrome c (cyt c) acts as a peroxidase; i.e., it catalyzes the oxidation of organic substrates by H₂O₂. This peroxidase function plays a key role during apoptosis. Typical peroxidases have a five-coordinate heme with a vacant distal coordination site that permits the iron center to interact with H₂O₂. In contrast, native cyt c is six-coordinate, as the distal coordination site is occupied by Met80. It thus seems counterintuitive that native cyt c would exhibit peroxidase activity. The current work scrutinizes the origin of this …

The Effect Of Different Heavy Metal Acetate Solutions On The Inhibition Of Catalase Enzyme, Athreya Murali, Sonali Patel

Journal of the South Carolina Academy of Science

The purpose of this experiment was to determine the effect of different aqueous solutions of ionic compounds on the rate of reaction of the enzyme catalase. The hypothesis states that zinc and cadmium acetate solutions will significantly inhibit catalase and its ability to produce oxygen. In the experiment, there were five trials performed with the lead acetate, zinc acetate, acetic acid, cadmium acetate, and distilled water (the last being the control group). In order to calculate the results, the ANOVA single factor test was used, comparing each solution to water. From results of the ANOVA test, it was found that …

The Effect Of Temperature On Zinc Leaching From Rubber Tire Mulch, Elizabeth Dillon

Journal of the South Carolina Academy of Science

Scrap tires are being recycled into many products in order to bypass slow degradation in landfills. Recycled rubber tire mulch contains zinc oxide used in tire formation that can be released through the creation of leachates. This study examines the relationship between temperature environment and leachate zinc concentration. After observing rubber mulch surface temperatures in conjunction with other factors, it was hypothesized that higher temperatures would lead to increased zinc release by rubber mulch and higher leachate zinc concentrations. Leachates were created by mixing 10 grams of mulch and 200 mL distilled water and placing in 5ºC, 29ºC, and 71ºC …

The Effects Of Tension, Curvature, And Lipid Diffusion On The Enrichment Of Ras Proteins In Model Membranes, Nina Daneshvar

Journal of the South Carolina Academy of Science

An intriguing aspect of the cell membrane that provokes study is lipid-anchor enrichment of lipidated proteins on the cell membrane. Specifically, recent in vitro studies involving the enrichment of Ras proteins were done to see how enrichment was affected by changes in membrane curvature. These studies demonstrated the Ras protein’s inclination to the expanded, or outer, leaflet of highly curved membranes. Other research done in vivo, however, provoked further inquiry into Ras protein behavior, since when highly curved protrusions were created in living cells, Ras proteins showed affinity for the inner leaflet. This inspired research to determine the exact mechanism …

Wake Up Barren Soil! Improving Enzymatic Function Of Contaminated Soils, Nina M. Goodey

Sustainability Seminar Series

A legacy of industrial use in metropolitan areas has left many soils contaminated with heavy metals and organic compounds. In some impacted soils, contaminants have altered the soils’ properties and ability to function. Soil microorganisms exude enzymes that break down nutrients, helping to nourish microorganisms and plants. Productive soils are often characterized by high enzymatic activities that are needed to convert decaying matter to plant nutrients. In soils where enzymatic function is low or nonexistent, plants may lack nutrients and fail to thrive. This case-study focuses on such a site within Liberty State Park in Jersey City, NJ, a brownfield …

Thermotropic Liquid-Crystalline Properties Of Extended Viologen Bis(Triflimide) Salts, Pradip K. Bhowmik, Shane T. Killarney, Jessa Rose A. Li, Jung Jae Koh, Haesook Han, Lewis Sharpnack, Deña M. Agra-Kooijman, Michael R. Fisch, Satyendra Kumar

Chemistry and Biochemistry Faculty Research

A series of extended, symmetric viologen triflimides were synthesised by the metathesis reaction of lithium triflimide with the respective viologen tosyalates in methanol. Their chemical structures were characterised by Fourier Transform Infrared, 1H and 13C Nuclear Magnetic Resonance spectroscopy and elemental analysis. Their thermotropic liquid-crystalline (LC) properties were examined by a number of experimental techniques including differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy and variable temperature X-ray diffraction. The viologen salts containing alkyl chain of two carbon and three carbon atoms were relatively low melting salts. Those of alkyl chains of four carbon and five carbon atoms formed ionic …

Self-Assembly Mechanisms Of Organosilanes And Porphyrins Investigated With Scanning Probe Microscopy, Phillip Charles Chambers Ii

LSU Doctoral Dissertations

This dissertation details the development of new fabrication strategies for the preparation of spatially selective surfaces by combining techniques of particle lithography and scanning probe microscopy (SPM). This combination of lithography and nanoscale surface characterization was applied to study the mechanisms of molecular level surface-assembly of organosilanes and porphyrin on surfaces of Si(111). Particle lithography was used to investigate the surface assembly of 4-chloromethylphenyltrichlorosilane (CMPS) within exposed sites of nanoholes in selected solvents and at selected temperatures to gain insight into the details of self-polymerization. Nanopillars of CMPS were generated under selected conditions of solvent and temperature and characterized with …

Table Of Contents

Journal of the South Carolina Academy of Science

No abstract provided.

Progress Toward Phidianidine Analogues Containing A 1,2,3-Triazole Ring, David Laws Iii, Dillon King, Bryan H. Wakefield

Journal of the South Carolina Academy of Science

Phidianidines are a class of compound that has been extracted from the sea mollusk Phidianis militaris. These compounds have been shown to exhibit a variety of useful properties such as antihistamine effects, anti-cancer activity, agonism of the µ-opioid receptor and neuroprotection. The biological activities are thought to be caused by the 1,2,4- oxadiazole ring found within the molecule. The goal of this project is to synthesize analogues of phidianidine that contain a 1,2,3-triazole instead of the 1,2,4 oxadiazole ring using a method that will allow for other regions of the molecule to be changed. This will help to elucidate …

The Effects Of Sports Related Head Impact On Balance And Neurocognitive Functions, Shaquanda D. Ross-Simmons, Michelle L. Vieyra, Abhishek Jain, Keri Weed

Journal of the South Carolina Academy of Science

The goal of this study was to investigate the effects of sports-related head injury on balance, attention, and memory. Reliable differences have been found using measures that directly tap into brain functioning, such as the auditory oddball task combined with EEG recording. We hypothesized that athletes reporting a diagnosed concussion or participation in high-risk sports would have compromised balance and neurocognitive functioning compared to athletes in low risk sports. Forty-five undergraduate participants were identified as either concussed, non-concussed in high-risk sports, or non-concussed in low-risk sports using a survey of athletic history, head trauma and demographics. The Biopac MP36 system, …

The Synthesis And Characterization Of Corannulene-Based Metal-Organic Frameworks, Marygrace H. Rainsford

Journal of the South Carolina Academy of Science

Due to the great demands within the energy community, the need to develop materials that can significantly alter the vitality of different substances is one of the top priorities of researchers. In recent years, metal-organic frameworks (MOFs) have been synthesized to potentially be used as these advances. The objective of this project is to specifically alter the synthetic route of corannulene-based MOFs to create a new anode for a Li-ion battery used in hybrid cars. Due to the crystalline materials porosity and high surface area, the rate performance of this battery can effectively be improved. To do this, a three …

Ensemble-Based Modeling And Rigidity Decomposition Of Allosteric Interaction Networks And Communication Pathways In Cyclin-Dependent Kinases: Differentiating Kinase Clients Of The Hsp90-Cdc37 Chaperone, Gabrielle Stetz, Amanda Tse, Gennady M. Verkhivker

Mathematics, Physics, and Computer Science Faculty Articles and Research

The overarching goal of delineating molecular principles underlying differentiation of protein kinase clients and chaperone-based modulation of kinase activity is fundamental to understanding activity of many oncogenic kinases that require chaperoning of Hsp70 and Hsp90 systems to attain a functionally competent active form. Despite structural similarities and common activation mechanisms shared by cyclin-dependent kinase (CDK) proteins, members of this family can exhibit vastly different chaperone preferences. The molecular determinants underlying chaperone dependencies of protein kinases are not fully understood as structurally similar kinases may often elicit distinct regulatory responses to the chaperone. The regulatory divergences observed for members of CDK …

Mechanistic Probes Of Zeolitic Imidazolate Framework For Photocatalytic Application, Brian Pattengale, Sizhuo Yang, Sungsik Lee, Jier Huang

Chemistry Faculty Research and Publications

In this work, we report a zeolitic imidazolate framework (ZIF-67) with remarkable activity in the hydrogen evolution reaction (HER): 40 500 μmol H₂/g of metal organic framework (MOF). This is, to the best of our knowledge, the highest activity achieved by any MOF system. This result necessitated assessment of the atomic-scale mechanistic function of ZIF-67 in HER, using advanced spectroscopy techniques, including time-resolved optical (OTA) and in situ X-ray-absorption (XAS) spectroscopy. Through the correlation of the OTA results with the catalytic performance, we demonstrated that the electron transfer (ET) pathway, rather than the energy transfer (ENT) pathway, between …

The Future Perspective: Metabolomics In Laboratory Medicine For Inborn Errors Of Metabolism, Yana Sandlers

Chemistry Faculty Publications

Metabolomics can be described as a simultaneous and comprehensive analysis of small molecules in a biological sample. Recent technological and bioinformatics advances have facilitated large-scale metabolomic studies in many areas, including inborn errors of metabolism (IEMs). Despite significant improvements in the diagnosis and treatment of some IEMs, it is still challenging to understand how genetic variation affects disease progression and susceptibility. In addition, a search for new more personalized therapies and a growing demand for tools to monitor the long-term metabolic effects of existing therapies set the stage for metabolomics integration in preclinical and clinical studies. While targeted metabolomics approach …

A Colorimetric Competitive Displacement Assay For The Evaluation Of Catalytic Peptides, Anneliese Gest, Erika M. Aguiluz, Malik T. Mays, Xinyu Liu, Eliza K. Neidhart, Leah S. Witus

Faculty Publications

No abstract provided.

Dendritic Plasmonics For Mid-Infrared Spectroscopy, Francois Lagugne-Labarthet, Gregory Q. Wallace, Hayden C. Foy, Scott M. Rosendahl

Chemistry Publications

Metallic nanostructures that exhibit tailored optical resonances spanning from the near to mid-infrared spectral range are of particular interest for spectroscopic and optical measurements in these spectral domains that can benefit from localized surface-enhancement effects. Plasmon resonances shifted in the near or mid-infrared range could be used to further enhance the excitation and/or the emission of an optical process. Surface-enhanced infrared absorption (SEIRA) is one of such processes and can particularly benefit from plasmon-enhanced local fields yielding an increase in sensitivity towards the detection of an analyte. Herein, we have fabricated a series of gold dendritic nanostructures, prepared by electron-beam …