Chemistry Commons^™

2021 Scas Annual Meeting Program And Bulletin

Journal of the South Carolina Academy of Science

No abstract provided.

Creation Of A Cip Method For The Heat Exchangers At Rolls-Royce, Melanie Howe, Austin Williams, Caroline Dempsey, Bethany Fralick

Journal of the South Carolina Academy of Science

Rolls-Royce produces various engines which must be tested prior to their distribution to ensure a high-quality product. The manufacturing plant contains four test cells where the engines can be subjected to high levels of torque and extreme temperatures. A heat exchanger is necessary in this testing system and over time, unwanted waste accumulates on the system’s plates. The team is tasked with developing and implementing a system mounted on a mobile cart which can provide data to determine whether the plates need to be cleaned. For this cleaning system to work, it must fully saturate the heat exchanger in cleaning …

The Effect Of Poverty Levels And Minority Percentages On Lead Content In South Carolina Midlands School Drinking Water, Kathleen L. Barfield

Journal of the South Carolina Academy of Science

No abstract provided.

Developing And Understanding Catalysts For Organic Synthesis, Shelby Dickerson

Theses and Dissertations

Organic synthesis relies on improving catalyst designs and understanding reaction mechanisms for the advancement of the field. This dissertation will describe projects in both of these areas. First it will cover new photocatalysts in the aim of maintaining reactivity while increasing solubility in less polar solvents, and second understanding the importance of intermolecular interactions between new nucleophilic catalysts and substrates.

Photocatalysis has become a major focus as a sustainable pathway for chemical reactions with visible light photocatalysts performing a large range of reactions such as redox reactions, cyclization reactions, and energy transfer reactions. Chapter 1 will discuss classes of organic …

Ahr Expression On Rorc-Expressing Immune Cells Is Essential For I3c-Mediated Protection Against Colitis, Michal C. Williams

Senior Theses

Colitis is an inflammatory bowel disorder (IBD) whose etiology is attributed to modification in the luminal microbiota and dysregulation in the immune response. Indole is a signaling molecule which is naturally produced by gut luminal microbiota. Indole-3- carbinol (I3C) is a compound commonly found in vegetables and a ligand for the aryl hydrocarbon receptor (AhR). Previous studies have detected decreased expression and activation on the AhR receptor in colitis patients, thought to possibly alter gut microbiota metabolism, subsequently promoting colitis. 1 AhR, expressed in a variety of immune and epithelial cells, contributes to gut homeostasis by affecting vital mediators such …

Characterization Of Ph – Responsive Nanocage Based On The Ferritin Iron Storage Protein, Satyam Singh

Theses and Dissertations

The iron-storage protein ferritin (Ftn) assembles into a protein cage structure with 24 subunits and octahedral (4-fold, 3-fold, 2-fold) symmetry. Each monomeric subunit contains a robust four-helix bundle fold. The fully assembled Ftn structure has a high degree of thermal stability (up to 100°C), a mono dispersed size (12 nm in diameter), and a large central cavity (7-8 nm in diameter). The central cavity stores ferric iron in phylogenetically diverse group of organisms, including humans. The central cavity has been used for encapsulation of cargoes such as other metals, contrast agents for imaging, small molecule drugs for therapy, …

Alkyne Cyclization Involving A Zwitterionic Hexaruthenium Carbido Carbonyl Complex And The Synthesis Of The First-Nitrido Heterometallic Carbonyl Cluster Complexes, Nutan Damodhar Wakdikar

Theses and Dissertations

Chapter 1 introduces two related topics with the primary focus on the background of zwitterions and the conceptual understanding of a metal-complexed zwitterion. It also discusses the potential of a metal-complexed zwitterion for a carbon-carbon bond formation reaction. Synthesis of the metal carbonyl cluster, Ru6(µ6-C)(µ-CO)(CO)16, is also discussed in detail. Then, the background with the importance of heterometallic cluster complexes is discussed with the help of various examples used for catalysis.

The reaction of hexaruthenium carbido carbonyl cluster, Ru6(µ6-C)(µ-CO)(CO)16, with C2H2 and Me3NO yielding first examples of two new zwitterionic complexes, Ru6C(CO)15(μ−η2−C2H2NMe3), 2.2, and Ru6C(CO)14(μ3−η4−C4H4NMe3), 2.3, are presented in Chapter …

Characterization Of A High Affinity Glutathione Transporter And Its Impact On Glutathione Depleted Saccharomyces Cerevisiae, Tirthankar Bandyopadhyay

Theses and Dissertations

Thiol-disulfide redox homeostasis is integral for maintaining the redox status of proteins and other thiol-containing molecules within the cell. Among the many antioxidants and detoxifying enzymes and small peptides, glutathione (GSH) has proven to be critical for the preservation of function and structural integrity of the cell due to its functionality in areas like oxidative protein folding, thiol redox control, reactive oxygen species (ROS) and xenobiotics removal as well as iron regulation and Fe-S cluster biogenesis. Therefore, our studies are aimed at elucidating the factors that control GSH trafficking and metabolism in the model eukaryote Saccharomyces cerevisiae (baker’s yeast). Using …

Exploration Of Vase As An Extraction Method For Emerging Disinfection By-Products And Acidic Methanol As A Safe And Effective Derivatization Method For Haloacids, Madison Leigh Kilpatrick

Theses and Dissertations

This project aims to create an environmentally friendly, robust, and efficient extraction and preconcentration method in both the detection and quantification of various disinfection by-products (DBPs). Vacuum assisted sorbent extraction (VASE) is a newly developed method in the extraction of both volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs). This extraction method is paired with a Thermo Scientific TSQ Quantum Triple Quadrupole GC-MS system for the quantification of DBPs. VASE outperforms current DBP extraction methods, with liquid-liquid extraction (LLE) being the most used alternative, because of its minimal use of solvent, high level of automation, and over-all ease of …

Plasmonic Metallic And Semiconductor Nanomaterials, Mengqi Sun

Theses and Dissertations

The earliest account of localized surface plasmon resonance (LSPR) has to date back to the ancient age of Rome in 400 A.D. The famous glass of Lycurgus cup told the story of unique light-and-matter interaction at the nanoscale that confines the electromagnetic field resonance at its surface and therefore allows LSPR feature to noticeably arise. The conventional metallic LSPR nanomaterials, like Au and Ag nanoparticles attract constant attentions due to their synthetic simplicity, chemical robustness, and visible spectral response. Its ability to generate sensitive dielectric sensing of the surroundings, strong electromagnetic field and active charge carriers upon optical excitation triggered …

Colloidal Semiconductor Quantum Dots: Solution Processing And Heterostructure-Based Optoelectronics, Mathew L. Kelley

Theses and Dissertations

Colloidal semiconductor quantum dots (QDs) are attractive candidates for high-efficiency solar cells and uncooled multiplexed photodetectors due to their favorable characteristics including large absorption cross-sections, size-tunable bandgap energies spanning the ultraviolet (UV) to short wave infrared, and solution processability. These QD-based optoelectronic devices operate on the basis of efficient photogenerated charge migration within QD solids and charge separation and recombination at electrical junctions, underscoring the need for (1) processing strategies that facilitate charge transport and (2) characterization techniques that robustly interrogate charge separation at QD interfaces. Here, my work on the post-synthetic processing and surface modifications of several semiconductor QDs, …

Free Three-Dimensional Carborane Carbanions, H.D.A. Zzzchathumal Jayaweera, Md. Mamdudur Rahman, Perry J. Pellechia, Mark D. Smith, Dmitry V. Peryshkov

Faculty Publications

Carbon atom functionalization via generation of carbanions is the cornerstone of carborane chemistry. In this work, we report the synthesis and structural characterization of free ortho-carboranyl [C₂B₁₀H₁₁]⁻, a three-dimensional inorganic analog of the elusive phenyl anion that features a “naked” carbanion center. The first example of a stable, discrete C(H)-deprotonated carborane anion was isolated as a completely separated ion pair with a crown ether-encapsulated potassium cation. An analogous approach led to the isolation and structural characterization of a doubly deprotonated 1,1′-bis(o-carborane) anion [C₂B₁₀H₁₀] …

Tailored Porous Carbons Enabled By Persistent Micelles With Glassy Cores, Eric R. Williams, Paige L. Mcmahon, Joseph E. Reynolds Iii, Jonathan L. Snider, Vitalie Stavila, Mark Allendorf, Morgan Stefik

Faculty Publications

Porous nanoscale carbonaceous materials are widely employed for catalysis, separations, and electrochemical devices where device performance often relies upon specific and well-defined regular feature sizes. The use of block polymers as templates has enabled affordable and scalable production of diverse porous carbons. However, popular carbon preparations use equilibrating micelles which can change dimensions in response to the processing environment. Thus, polymer methods have not yet demonstrated carbon nanomaterials with constant average template diameter and tailored wall thickness. In contrast, persistent micelle templates (PMTs) use kinetic control to preserve constant micelle template diameters, and thus PMT has enabled constant pore diameter …

Host–Guest Interactions In A Metal–Organic Framework Isoreticular Series For Molecular Photocatalytic Co2 Reduction, Philip M. Stanley, Johanna Haimerl, Christopher Thomas, Alexander Urstoeger, Michael Schuster Prof. Dr., Natalia B. Shustova Prof. Dr., Angela Casini Prof. Dr., Bernhard Rieger Prof. Dr., Julien Warnan Dr., Roland A. Fischer Prof. Dr.

Faculty Publications

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3(4,4′-dcbpy)] and a photosensitizer [Ru(bpy)2(5,5′-dcbpy)]Cl2 using the isoreticular series of metal–organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location—either at the outer MOF particle surface or inside the MOF cavities—affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, …

Beyond Structural Motifs: The Frontier Of Actinide-Containing Metal–Organic Frameworks, Corey R. Martin, Gabrielle A. Leith, Natalia B. Shustova Prof. Dr.

Faculty Publications

In this perspective, we feature recent advances in the field of actinide-containing metal–organic frameworks (An-MOFs) with a main focus on their electronic, catalytic, photophysical, and sorption properties. This discussion deviates from a strictly crystallographic analysis of An-MOFs, reported in several reviews, or synthesis of novel structural motifs, and instead delves into the remarkable potential of An-MOFs for evolving the nuclear waste administration sector. Currently, the An-MOF field is dominated by thorium- and uranium-containing structures, with only a few reports on transuranic frameworks. However, some of the reported properties in the field of An-MOFs foreshadow potential implementation of these materials and …

Beyond Structural Motifs: The Frontier Of Actinide-Containing Metal–Organic Frameworks, Corey R. Martin, Gabrielle A. Leith, Natalia B. Shustova

Faculty Publications

In this perspective, we feature recent advances in the field of actinide-containing metal-organic frameworks (An-MOFs) with a main focus on their electronic, catalytic, photophysical, and sorption properties. This discussion deviates from a strictly crystallographic analysis of An-MOFs, reported in several reviews, or synthesis of novel structural motifs, and instead delves into the remarkable potential of An-MOFs for evolving the nuclear waste administration sector. Currently, the An-MOF field is dominated by thorium- and uranium-containing structures, with only a few reports on transuranic frameworks. However, some of the reported properties in the field of An-MOFs foreshadow potential implementation of these materials and …

The Supercam Instrument Suite On The Mars 2020 Rover: Science Objectives And Mast-Unit Description, S. Maurice, R. C. Wiens, P. Bernardi, P. Caïs, S. Robinson, T. Nelson, O. Gasnault, J. -M. Reess, M. Deleuze, F. Rull, J. -A. Manrique, S. Abbaki, R. B. Anderson, Y. André, Stanley M. Angel, G. Arana, T. Battault, P. Beck, K. Benzerara, S. Bernard, Et. Al.

Faculty Publications

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2–7 m, while providing data at sub-mm to mm scales. We report …

Broken-Hearted” Carbon Bowl Via Electron Shuttle Reaction: Energetics And Electron Coupling, Gabrielle A. Leith, Allison M. Rice, Brandon J. Yarbrough, Preecha Kittikhunnatham, Abijai Mathur, Nicholas A. Morris, Megan J. Francis, Anna A. Berseneva, Poonam Dhull, Richard D. Adams, M. Victoria Bobo, Aaron A. Vannucci, Mark D. Smith, Sophya Garashchuk, Natalia B. Shustova

Faculty Publications

Unprecedented one-step CC bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such …

Raman Spectroscopy Using A Monolithic Spatial Heterodyne Raman Spectrometer For Planetary Exploration, Abigail M. Waldron

Theses and Dissertations

Raman spectroscopy is a vibrational technique that provides detailed molecular and structural information for organic and inorganic molecules and minerals, and is uniquely suited for spacecraft applications, in the search for chemical indicators of life. This is why NASA sent two Raman spectrometers to Mars on the Mars 2020 Perseverance rover, as part of the SuperCam and SHERLOC instruments. The Raman spectrometers on Perseverance are conventional dispersive instruments that have been engineered to survive the harsh conditions of spaceflight. Future missions could benefit from smaller, more robust designs, especially missions to the Jovian planets, Jupiter and Saturn, their moons, asteroids …

Development Of A Liquid Biopsy: Using A Synthetic Lectin Array For The Detection Of Cancer, Mary Grace Hollenbeck

Theses and Dissertations

Cancer is the second leading cause of death worldwide with 9.6 million deaths in 2019. It is well known that early detection of cancer often leads to a better prognosis. However, due to drawbacks associated with current cancer screens (i.e. invasiveness, high false positive and negative rates) new or updated early detection methods are needed. Chapter one overviews current breast, colon, and prostate detection methods and the drawbacks associated with them. Additionally, this chapter presents an alternative detection method that utilizes an array of boronic acid functionalized synthetic lectins. We describe the development and progression of this array and show …

Conservation Of Polyester-Urethane Magnetic Audio Tapes And Discrimination Of Textile Fiber Dyes Using Spectroscopy And Chemometrics, Nilmini Hemanthika Ratnasena

Theses and Dissertations

This dissertation explores and discusses conservation of magnetic audio tapes and discrimination of fiber dyes employing spectroscopic techniques and chemometrics.

Conservation of polyester urethane magnetic audio tapes has become a major challenge since they are susceptible to degradation via hydrolysis. The world’s modern cultural history is vastly recorded in this media, and now conservationists need a non-destructive technique to determine the playability status of these tapes. Once conservationists identify degraded tapes, they can be subjected to the baking process. This process temporarily reverses hydrolysis and provides enough time to digitize tapes, preserving information for future generations. The first three chapters …

Molecular Basis Of Xenobiotic Metabolism And Resistance In Tetranychus Urticae, Leily Daneshian

Theses and Dissertations

Invasive pest species are a major cause of crop loss around the world and adversely affect the agricultural industry. We are focusing on Tetranychus urticae (two-spotted spider mite; TSSM), which is a polyphagous pest that targets more than 1100 plant species. The TSSM alone causes a loss of roughly $1.6 billion per year globally due to acaricide resistance. It is developing resistance to most acaricides due to rapid growth and reproduction. Therefore, new acaricides are needed to combat TSSM resistance and infestation [1]. To address this problem, four enzymes of TSSM, intradiol ring cleavage dioxygenases, a glutathione S-transferase, a β …

Fate Of Persistent Contaminants And Emerging Algal Toxins In Drinking Water And The Environment, Danielle Christine Westerman

Theses and Dissertations

Population growth and global climate change has resulted in the degradation of pristine water sources, causing issues like saltwater intrusion, persistent harmful algal blooms, and drought from population growth. Future reliance on alternative sources of drinking water to is expected globally, therefore, nontraditional sources of drinking water are becoming increasingly vital sources of potable water around the world. For example, desalination (typically by reverse osmosis), despite its high energy demands and high cost, is being utilized all over the world to meet drinking water demand. Wastewater reuse, the additional treatment of wastewater to produce drinking water, either directly or indirectly, …

Studies Of The Chemistry Of Pentaruthenium Carbido Carbonyl Cluster Complexes With Aldehydes, Azobenzene And Alkynes, Humaiara Akter

Theses and Dissertations

Polynuclear metal carbonyl complexes serve as the bridging model between heterogeneous catalysis and homogeneous catalysis for the activation of small molecules. Ru5(m5-C)(CO)15 has been found to exhibit superior reactivity due to its unusual polynuclear metal geometry. possibilities of interconversions of ligand bonding modes, and the formation of the electronically unsaturated metal species. C-H activation in aldehydes and azobenzene of pentaruthenium cluster complexes is described in chapters 2 and 3 respectively. The formation of new hydrocarbyl zwitterions and C – C coupling ethyne to the carbido carbon in the complex, and the alkyne insertion reactions with pentaruthenium cluster complexes are described …

Cationic Metallo-Polyelectrolytes: Synthesis And Application In Self-Assembly And Mechanochemistry, Yujin Cha

Theses and Dissertations

In this dissertation, cationic metallocene-containing polyelectrolytes were investigated for the construction of nano-objects by CDSA and the mechanical force-responsive polymer. The self-assembly behavior and mechanically induced polymer deformation were characterized and discussed.

In Chapter 1, the overall background and recent development of metallocene-containing polymers as well as their applications in self-assembly and polymer mechanochemistry were introduced. Primary research objectives were described.

The first section of the dissertation on the CDSA of cationic metallocene-containing block copolymers was provided in Chapter 2. The preparation of PCL-b-PCoAEMAs was achieved through ring-opening polymerization (ROP) of ε-caprolactone and reversible addition-fragmentation chain-transfer (RAFT) polymerization of cobaltocenium …

Sparse Modeling For Predicting Class Assignments For Trace Forensic Evidence, Dayla Christine Rich

Theses and Dissertations

Numerous disciplines in forensic science utilize various types of spectral data when analyzing evidence. Spectral techniques are particularly critical for the analysis of trace evidence, as these methods are normally non-destructive. Preserving evidence, especially trace evidence, is of high priority in a forensic laboratory setting. Once a piece of evidence has been fully consumed, no more analyses can be performed. Typically, visual comparison, or spectral overlay, is performed to compare questioned samples (evidence) to standards or knowns. However, such an approach may not be optimal in distinguishing the subtle, yet highly important, discriminating characteristics present in the spectra. As statistical …

Characterization And Hydrogenation Activity Of Supported Palladium Particles, Narayan Acharya

Theses and Dissertations

In this project, the hydrogenation activity of palladium (Pd) particles supported on different carbon and oxide supports was investigated. Supported Pd particles were prepared using strong electrostatic adsorption (SEA) technique, which is known to produce metal particles with narrow and uniform distribution. The scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), and chemisorption methods were used to characterize the Pd particle size in this project. The Pd particles on different supports were annealed at a specific temperature, and the particle size was studied as a function of annealing temperature. Propylene hydrogenation to propane was conducted in a flow reactor to …

Functional Supramolecular Materials And The Design And Synthesis Of Triple Negative Breast Cancer Pharmaceuticals, Dustin Wayne Goodlett

Theses and Dissertations

Organization of benzophenone in the solid-state facilitates the formation of persistent and regenerable radicals at room temperature upon exposure to light. Upon incident irradiation, the triplet sensitizer rapidly undergoes intersystem crossing to a triplet excited state. Structural investigation of four distinct benzophenone supramolecular assemblies gives insight into the different processes these materials can undertake once in the triplet excited state such as persistent radical formation, phosphorescence, and self-quenching.

Self-assembly of brominated triphenyl amine bis-urea macrocycles forms a host material with unidirectional pores. Separations of xylene constitutional isomers via adsorption within this crystalline host material at ambient temperature are shown to …

Effect Of Oil And Gas Extraction On Disinfection By-Product Formation In Drinking Water, Dallas Graham Abraham

Theses and Dissertations

Certain industrial processes, such as energy extraction and utilization, generate massive amounts of wastewater with various geogenic and synthetic contaminants. Oil and gas wastewaters are characterized by elevated halide levels, particularly geogenic bromide and iodide. Concentrations in produced wastewaters have been reported as high as thousands of mg/L of bromide and tens of mg/L of iodide. Large volumes of these wastewaters are stored, transported, and disposed of, potentially impacting drinking water sources. Because conventional wastewater treatment fails to remove halides, oil and gas wastewater disposal, even after treatment, facilitates the formation of brominated and iodinated disinfection by-products (DBPs) at downstream …

Automating And Implementing Complex, Multistep Sample Preparation Processes To Generate Reproducible Proteomic And Phosphoproteomic Data, Brian Todd Mullis

Theses and Dissertations

Phosphorylation is the most common post-translational modification that occurs within the cell and is intricately involved in many biological processes. It is important to understand the roles that protein kinases and phosphatases play by mapping protein phosphorylation as many disease states stem from aberrant signaling events. With the advent of modern mass spectrometry (MS), researchers are now provided with more complex phosphorylation patterns from thousands of proteins in each mass spectrometric analysis. Further developments in quantification techniques, such as stable isotope labeling with amino acids in cell culture (SILAC) and label-free quantitation, have allowed researchers to reliably quantify changes to …