Chemistry Commons^™

Nickel Exposure Reduces Enterobactin Production In Escherichia Coli, Clorissa L. Washington-Hughes, Geoffrey T. Ford, Alsten D. Jones, Kimberly Mcrae, Franklin Wayne Outten

Faculty Publications

Escherichia coli is a well- studied bacterium that can be found in many niches, such as industrial wastewater, where the concentration of nickel can rise to low- millimolar levels. Recent studies show that nickel exposure can repress pyochelin or induce pyo-verdine siderophore production in Pseudomonas aueroginosa. Understanding the mo-lecular cross- talk between siderophore production, metal homeostasis, and metal toxicity in microorganisms is critical for designing bioremediation strategies for metal- contaminated sites. Here, we show that high- nickel exposure prolongs lag phase duration as a result of low- intracellular iron levels in E. coli. Although E. coli cells respond to low- …

Nickel Exposure Reduces Enterobactin Production In Escherichia Coli, Clorissa L. Washington – Hughes, Geoffrey T. Ford, Alsten D. Jones, Kimberly Mcrae, Franklin W. Outten

Faculty Publications

Escherichia coli is a well- studied bacterium that can be found in many niches, such as industrial wastewater, where the concentration of nickel can rise to low- millimolar levels. Recent studies show that nickel exposure can repress pyochelin or induce pyo-verdine siderophore production in Pseudomonas aueroginosa. Understanding the mo-lecular cross- talk between siderophore production, metal homeostasis, and metal toxicity in microorganisms is critical for designing bioremediation strategies for metal- contaminated sites. Here, we show that high- nickel exposure prolongs lag phase duration as a result of low- intracellular iron levels in E. coli. Although E. coli cells respond to low- …

Identification Of Coliphages In The Aviary At Brookgreen Gardens And The Factors That Might Influence Coliphage Population Dynamics In This Cypress Swamp Environment, Olivia Shirley, Lisa Pieterse, Paul E. Richardson

Journal of the South Carolina Academy of Science

It has been understood that the presence of coliphages (bacteriophages specific for E. coli) in water is an indirect measurement of fecal contamination. Bacteriophages have been suggested to hold an important role in regulating the bacterial population. This pilot study analyzes the relationship between the presence of coliphages in the water in the aviary at Brookgreen Gardens and how environmental factors such as temperature, pH, and turbidity affect the presence of these viruses over the time period of three months (June 2017 through August 2017). Coliphages found in volary water sources were speculated to be deposited directly by birds that …

An Investigation Of The Order Of Applying An Emollient With A Topical Steroid In The Treatment Of Atopic Dermatitis, Andrea Conner, Ashlee Tietje

Journal of the South Carolina Academy of Science

In 2007, the prevalence of Atopic Dermatitis had increased two to three-fold within the last three decades and affected 15-20% of young children (Buys, 2007). Current treatment includes the use of both steroid and emollient creams. Current suggestions for the order of application are contradictory. This study aims to examine the role of the order of application of treatments for Atopic Dermatitis (AD). Hairless mice (SKH-1) were induced to a mild AD flare-up using 2,4-dinitrochlorobenzene (DNCB) and treated with either 1% hydrocortisone (Maximum Strength Cortizone 10 cream) alone, 1% hydrocortisone followed by Cetaphil (emollient), or Cetaphil followed by 1% hydrocortisone. …

Investigating The Lytic Staphylococcus Aureus Bacteriophage Reservoir Amongst A South Carolina University Population: Discovery, Characterization, And Identification Of A Potential Bacteriophage Treatment For Methicillin-Resistant Staphylococcus Aureus, Lisa Pieterse, Amy Powers, Derek Pride, Lisha Van Onselen, Giovanna E. Leone, Paul E. Richardson

Journal of the South Carolina Academy of Science

Bacteriophages are viruses that only infect bacterial cells and can be used to treat antibiotic resistant bacterial infections. This study focused on the isolation and characterization of bacteriophages lytic to Staphylococcus aureus at Coastal Carolina University (CCU) in Conway, South Carolina, as a means to isolate bacteriophages that can potentially be used to treat methicillin-resistant Staphylococcus aureus (MRSA), an antibiotic-resistant S. aureus variant. From 2014 to 2018, collection of ear and nose samples from 225 randomly selected CCU volunteers was conducted. Filter sterilization, amplification, microbial tests, and PCR analyses were performed in order to identify and characterize bacteriophages. Coliphage populations …

Table Of Contents

Journal of the South Carolina Academy of Science

No abstract provided.

Building Soft Nanomachines From Polydiacetylene Liposomes, Timothy W. Hanks

Journal of the South Carolina Academy of Science

No abstract provided.

Hydrogen Sulfide Gas Detection Via Multivariate Optical Computing, Bin Dai, Christopher Michael Jones, Megan Pearl, Mickey Pelletier, Michael L. Myrick

Faculty Publications

Hydrogen-sulfide gas is a toxic, colorless gas with a pungent odor that occurs naturally as a decomposition by-product. It is critical to monitor the concentration of hydrogen sulfide. Multivariate optical computing (MOC) is a method that can monitor analytes while minimizing responses to interferences. MOC is a technique by which an analogue calculation is performed entirely in the optical domain, which simplifies instrument design, prevents the drift of a calibration, and increases the strength and durability of spectroscopic instrumentation against physical perturbation when used for chemical detection and identification. This paper discusses the detection of hydrogen-sulfide gas in the ultraviolet …

Facially Amphiphilic Polyionene Biocidal Polymers Derived From Lithocholic Acid, Mitra S. Ganewatta, Md Anisur Rahman, Louis Mercado, Tinom Shokfai, Alan W. Decho, Theresa M. Reineke, Chuanbing Tang

Faculty Publications

Bacterial infections have become a global issue that requires urgent attention, particularly regarding to emergence of multidrug resistant bacteria. We developed quaternary amine-containing antimicrobial poly(bile acid)s that contain a hydrophobic core of lithocholic acid in the main-chain. Interestingly, by choosing appropriate monomers, these cationic polymers can form core-shell micelles. These polymers exhibited biocidal activity against both Gram-positive and Gram-negative bacterial species. It is demonstrated that the micelles can deliver hydrophobic antibiotics that functionally have dual antimicrobial activities. Cytotoxicity assays against HeLa cells showed dosage-dependent toxicity for polymers with longer linkers.

Advancing Professional Development Strategies For Chemistry And Biochemistry Undergraduates, Christian A. Brown

Senior Theses

In the Department of Chemistry and Biochemistry at the University of South Carolina (the Department), most curriculum-driven professional development is reserved for third- and fourth-year students. Classroom learning occurs at all levels, but the context comes late. Early exposure to career options and hands-on training is imperative for undergraduates to obtain maximum experiential learning. The purpose of this project is to advance the current professional development strategies of the Department, specifically targeting second- and third-year students. The study surveyed students' current involvement in professional development activities. The data on extracurricular experience and post-graduation interest was used to design a workshop …

Expansion Of The (Bb)>Ru Metallacycle With Coinage Metal Cations: Formation Of B-M-Ru-B (M= Cu, Ag, Au) Dimetalacyclodiboryls†, Bennett J. Eleazer, Mark D. Smith, Alexey A. Popov, Dmitry V. Peryshkov

Faculty Publications

In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium–boron bonds on a surface of icosahedral boron clusters. M(I) cations (M ¼ Cu, Ag, and Au) insert into B–Ru bonds of the (BB)–carboryne complex of ruthenium with the formation of four-membered B–M–Ru–B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B–M/Ru interactions that are isolobal to B–H/Ru borane coordination for M ¼ Cu and Ag, or the pairs of two-center-two electron B–Au and Au–Ru …

Investigation Of The Spatial Dependence Of Carrier Dynamics In Semiconductor Optoelectronic Devices, Bobby G. Barker Jr.

Theses and Dissertations

Optoelectronic devices, such as solar cells and photodetectors, rely on separating and transporting charge through semiconductors that have excess electron-hole pairs created by photon absorption. This talk will focus of several different semiconductor materials of various dimensionality, such as lead halide perovskites, wide bandgap SiC, graphene, semiconductor nanowires (NWs), and quantum dots (QDs).

The results of Chapter 2 demonstrate the dependence of the perovskite/hole transport layer on carrier transport of perovskite films for solar cells. Efficient charge separation at the interfaces of the perovskite with the carrier transport layers is crucial for perovskite solar cells to achieve high power conversion …

Iron Transport Machinery: A Potential Therapeutic Target In Escherichia Coli, Clorissa L. Washington – Hughes

Theses and Dissertations

Iron metabolism is an integral part of life for most organisms. Despite its essentiality, iron can also become toxic. There are many aspects to maintaining iron balance within the cell. The aim of this work is to provide insight into the function of several components involved in bacterial iron homeostasis. This work is significant for the development of novel antibiotics for treating resistant or pathogenic bacteria. Herein, it is shown that nickel can disrupt normal bacterial iron metabolism and that bacterial resistance can be affected by expression of iron acquisition genes. Once iron is obtained by the cell, it can …

Block Copolymer Control Of Nanoscale Porous Materials, Amrita Sarkar

Theses and Dissertations

The controlled fabrications of porous materials are crucial for a wide variety of uses spanning the gamut from energy applications to filtration. Despite decades of developments based upon block copolymer self-assembly there remain numerous limitations to achieve simple ends such as fully-tunable nanomaterials or well-defined macroscopic forms. For example, fundamental studies of nanostructure-performance relationships need systematic series of nanomaterials to identify the separate effects of wall and pore dimensions. Such precision control is impossible under the constraints of equilibrating systems. Persistent Micelle Templating (PMT) is rather based on kinetic control and enables robust and independent tuning of each feature. However, …

Hydrothermal Synthesis: A Gateway To Metastable Crystals With Unusual Properties, Justin B. Felder

Theses and Dissertations

Research into crystalline matter has long been of interest to humanity, both in order to advance our society by creating new technologically useful materials and in order to better understand to nature of the properties we depend on for so much of our existing technology. In recent decades, solution-based crystal growth syntheses including hydrothermal and molten flux techniques have risen to the forefront of solid-state chemistry as superior methods of synthesizing new materials as single crystals ripe for structure determination and property measurements.

This work seeks to educate readers on recent advances in the hydrothermal realm of crystal growth: namely …

Electrochemical Methods To Study Real-Time In Vivo Neurochemistry, Aya Abdalla

Theses and Dissertations

Serotonin neurotransmission has multiple facets that are challenging to characterize, due to the lack of analytical tools that can measure serotonin in the brain. In addition, the mechanisms of serotonin modulation by other neurotransmitters, such as histamine, are not well understood. These limitations make the study and treatment of disorders in which serotonin is implicated problematic. This dissertation presents novel electrochemical methods, in addition to the well-established serotonin fast-scan cyclic voltammetry (FSCV), to better understand the dynamics of serotonin and histamine neurotransmission in vivo. In Chapter 1, a method, known as fast-scan controlled adsorption voltammetry, was optimized to selectively and …

Crystallomagnetic Studies Of First And Third Row Transition Metal Containing Oxides Grown Via The Molten Flux Method, Timothy Ferreira

Theses and Dissertations

The primary objective of this dissertation is to inform about the single crystal growth of complex first and third row transition metal oxides via molten flux methods. Particular focus is given to complex oxides that contain transition metals with unpaired electrons. This fundamental research is motivated by a singular question: What can a critical analysis of chemical structure elucidate about magnetic order in oxide materials? Throughout the eight chapters of this dissertation, including an introductory chapter, this structure-property relationship will be investigated. These seven chapters will be organized into three parts, each corresponding to the general structure type of the …

Tailoring Polybenzimidazole Membranes For Enhanced Performance In Electrochemical Devices, Andrew T. Pingitore

Theses and Dissertations

After approximately 15 years of development, polybenzimidazole (PBI) chemistries and the concomitant manufacturing processes have evolved into commercially produced membrane electrode assemblies (MEAs). PBI MEAs can operate reliably without complex water humidification hardware and are able to run at elevated temperatures of 120-180 OC due to the physical and chemical robustness of PBI membranes. These higher temperatures improve the electrode kinetics and conductivity of the MEAs, simplify the water and thermal management of the systems, and significantly increase their tolerance to fuel impurities. Membranes cast by a newly developed polyphosphoric acid (PPA) Process possessed excellent mechanical properties, higher phosphoric acid …

Dually Modified Transmembrane Proteoglycan Tβriii/Betaglycan In Cell Signaling And Cancer, Laura M. Jenkins

Theses and Dissertations

During tumor progression, cancer cells undergo a number of alterations to evade tumor inhibitory mechanisms, proliferate, invade surrounding tissues and metastasize to distant sites. These properties reflect changes in their cell signaling pathways that, in normal cells, control aberrant cell proliferation, motility, and survival. Over the past few decades, hyperactive Wnt/β-catenin signaling has been linked to the formation of multiple cancers, including malignant ovarian cancer, making identification of molecules regulating Wnt/β-catenin signaling crucial to the development of early detection methods and cancer treatment strategies. Proteoglycans, which regulate transmission of cellular signals, are implicated in the pathophysiology of diseases, including cancer, …

Fabrication And Application Of Functional Polymer-Protein Coreshell Nanoparticles, Lin Lu

Theses and Dissertations

The study of polymer-protein nanoparticles is of increasing interest due to their various potential applications in biosensing, imaging, bioseparations, gene and drug delivery, etc. Synthetic polymers can be tailored with different functional groups and properties, therefore, they can serve as platforms to impart proteins with additional features and assist proteins to better perform biological functions. In this dissertation work, we were mainly focusing on the preparation of polymer-protein core-shell nanoparticles by synthesizing new functional polymers and assembling them with proteins for different applications. In chapter 1, a pyridine grafted diblock copolymer P(CL-g-Py)-b-PCL was prepared through ROP and CuAAC reactions. …

Structural Transformations Of Multimetallic Nanoparticles, Guangfang Li

Theses and Dissertations

Atomic-level understanding of the structural transformations of multimetallic nanoparticles (NPs) triggered by external stimuli is of vital importance to the enhancement of our capabilities to precisely fine-tailor the key structural parameters and thereby to fine-tune the catalytic properties of the NPs. In this work, I firstly show that Au-Cu bimetallic NPs demonstrate stoichiometry-dependent architectural evolutions during chemical dealloying processes and nanoporosity-evolving percolation dealloying only occurs for Au-Cu alloy NPs with Cu atomic fractions above the parting limit. The electrochemically active surface area and the specific activity of the dealloyed nanoframes can be systematically tuned to achieve the optimal electrocatalytic activity. …

Probing Solvent Effects In Aromatic Interactions Using Molecular Balances, Josef M. Maier

Theses and Dissertations

Aromatic interactions play a key role in many important processes, such as the formation and stability of biological and synthetic assemblies, facilitation of molecular recognition processes, and catalysis of chemical reactions. One of the key factors determining the strength of aromatic interaction is the solvent environment. Therefore, developing model systems that can accurately measure the influence or effects of solvents on non-polar interaction strengths is a task of great importance. Over the years, we have been approaching this challenge via designing and analyzing molecular devices that can quantitatively report aromatic interaction energies under various solvent and chemical environments. With this …

Synthesis Of Small-Molecule Fluorescent Probe And Polymers For Bioapplication: Bioimaging And Enzyme Stabilization, Yanmei Xu

Theses and Dissertations

In chapter one, we designed, synthesized and characterized two cysteine sensors CCPAP and CCPAN, with improved water solubility, cell penetration ability, and potential targeting selectivity. Two types of positive charged groups, i.e. triphenylphosphonium and pyridinium were introduced respectively to the frame structure CCP by coupling carboxylic acid with amine to improve the cell permeability and cysteine selectivity. ESI-MS, NMR and IR were employed to characterize the molecular structures of the two novel probes. These probes have better water solubility than the parent molecule DCP, and better cell penetration capability than CEP, which could further distinguish the cysteine concentration differences in …

Mechanisms Of Decarboxylation In The Cyp152 Family Of Cytochrome P450s, José Armando Amaya

Theses and Dissertations

Intense interest has focused on the development of enzymes as next-generation catalysts for the production of molecules with biotechnological potential. OleTJE, a member of the cytochrome P450 CYP152 family is an excellent candidate for the generation of advanced biofuels. OleTJE catalyzes the hydrogen peroxide-dependent decarboxylation of Cn fatty acids to produce Cn-1 terminal alkenes. Despite the ability of this enzyme to yield long chain alkenes with nearly exclusive chemoselectivity, its reactivity towards shorter chain length substrates results in undesired levels of hydroxylated side-products, limiting its industrial potential. Previous transient kinetic studies have demonstrated that, despite its unusual chemistry, the reaction …

Instrumentation For, And Application Of, Novel Electrochemical Tools For In Vivo Analysis Of Neurotransmitters In The Context Of Psychiatric Disease, Rhiannon Robke

Theses and Dissertations

ABSTRACTSerotonin’s involvement in many physiological processes including anxiety, stress, compulsivity, and mood has been speculated for decades. Insufficient progress in our understanding of serotonin chemistry is due to the lack of effective tools to selectively measure this neurotransmitter on a neurotransmission-relevant time scale in vivo. An analytical technique for serotonin measurements, fast-scan cyclic voltammetry (FSCV), was pioneered in the last decade in anesthetized rodents and is beginning to shed light on the complexity of serotonergic activity on a sub-second timescale. Complementary, more recent technological innovations have enabled ambient neurotransmitter levels to be determined every few seconds using a method called …

Understanding The Adsorption And Nucleation Of Transition Metals On A Model Carbon Support, Grant S. Seuser

Theses and Dissertations

Heterogeneous catalysis plays a vital role in the commercial production of chemicals. However, much is still unknown about the fundamental surface chemistry involved in catalyst preparation and the surface chemistry of the catalysts themselves. In the first part of this work, a surface science approach was employed to develop a fundamental understanding of the surface chemistry of strong electrostatic adsorption (SEA) of metal precursors on a model carbon support, highly oriented pyrolytic graphite (HOPG). SEA is a wet impregnation method in which anionic/cationic metal precursors are adsorbed onto positively/negatively charged functional groups by adjusting the pH of the solution above …

Studies Of The Activation Of Carbon-Gold And Carbon-Hydrogen Bonds By The Pentaruthenium Carbonyl Cluster Ru5(Μ5-C)(Co)15, Jonathan Darrell Tedder

Theses and Dissertations

The current practical uses of hydrocarbons by industry are discussed in Chapter 1. Carbon-hydrogen (C-H) bond activation and selective functionalization by transition metal complexes is presented as a possible alternative for the upgrading of hydrocarbons. The comparison of carbon-gold (C-Au) bond activation to C-H bond activation based on isolobal principles by transition metal complexes is presented. The high nuclearity ruthenium cluster complexes Ru6C and Ru5C are presented and their early chemistry is discussed.

The reactions of high nuclearity carbido cluster complexes, Ru6C(CO)17 and Ru5C(CO)15, with PhAuNHC are presented in Chapter 2. The reaction of Ru6C(CO)17 with PhAuNHC yields the π-arene …

Multiple C-H Bond Activations Of Aromatic Compounds By Unsaturated Dirhenium Carbonyl Complexes, Poonam Dhull

Theses and Dissertations

The background and importance of aromatic C-H bond activation by metal complexes are discussed in Chapter 1 with the help of various examples from the literature. Synthesis of the dirhenium complex Re2(CO)8(-C6H5)(-H) 1.1 is also discussed in detail. It also includes work done on C-H activation on arenes and heteroarenes by previous members of Dr. Adams’ group. The reactions of Re2(CO)8(-C6H5)(-H) with naphthalene and anthracene yielding the first multiply-CH activated arene products by the multiple oxidative-addition processes are presented in Chapter 2. The reaction of Re2(CO)8(-C6H5)(-H) with itself yielded the doubly-Re2-metalated C6H4 bridged compound Re2(CO)8(µ-H)(µ-1,µ-3- C6H4)Re2(CO)8(µ-H), 2.3. The reaction of …

Inorganic Nanocrystals And Their Applications In Hybrid 0d:2d Material Optoelectronics, Mathew Kelley

Theses and Dissertations

Functional nanomaterials have garnered great interest as candidates for use in next-generational optoelectronics such as solar photovoltaics, light-emitting diodes, and photodetectors. Among these low-dimensional materials, hybrid devices employing both 0D and 2D materials are of interest due to exploitation of the favorable characteristics of each component, and performances superior to standalone counterparts are achievable. This thesis is divided into two parts, as follows. The first two chapters will introduce lowdimensional materials and their favorable characteristics; our work on the formation of ligand-exchanged nanocrystal thin films purified by gel-permeation chromatography will also be discussed. In the second component, the formation and …

Hierarchical Corannulene-Based Materials, Allison M. Rice

Theses and Dissertations

Merging the intrinsic properties of fullerene (buckyball) and corannulene (buckybowl) derivatives with the inherent properties of crystalline metal- and covalentorganic frameworks (MOFs and COFs), including their modularity, porosity, versatility, high surface area, and structural tunability, opens a pathway to unlock a novel class of fulleretic materials. Despite the great interest in MOFs and COFs, as well as fullerene derivatives, this dissertation is focused on crystalline fullerene- and corannulenecontaining frameworks, highlighting their potential contributions in the fields of optoelectronic devices, electrodes, and photosensitizers. We have revealed a dual role of fullerene- and corannulene-containing building blocks showing their versatility to act as …