Chemistry Commons^™

Sustainable Soybean Oil And Lignin Derived Monomers And Polymers For Potential Use In Polymeric Materials, Ryan Miskin

Theses and Dissertations

In this thesis project, high oleic soybean oil and lignin derived monomers and polymers are investigated. The properties of these monomers and polymers are characterized and discussed.

Chapter 1 details the potential impact of bio-based resources, monomers, and polymers on the environment. An introduction on polymerization techniques is given, and the overall objectives of my research are discussed.

In Chapter 2, attempts are made at modifying a soybean oil derived thermoplastic polymer into a vitrimer. The synthesis of thermoplastics is reviewed and the vitrimer trials outlined. Different scenarios that arose are examined and discussed.

Chapter 3 outlines the preparation of …

Cationic Metallocene-Containing Biomaterials For Antimicrobial Applications, Parasmani Pageni

Theses and Dissertations

Metal-containing polymers or metallopolymers, are one of the major classes of polymers which stand out independently because of a unique combination of organic and inorganic components in one macromolecular system. Among the variety of metallopolymers, metallocene-containing polymers have been widely utilized for applications ranging from electrochemical sensors to templates for advanced inorganic catalysts to battery materials, due to their unique physicochemical properties. This dissertation is focused on the synthesis, characterization, and application of cationic metallocene-containing polymeric materials. Cationic-cobaltocenium was grafted in various inorganic nanoparticles using polymerization techniques such as reversible addition-fragmentation chain transfer polymerization.

In Chapter 1, the overall background …

Construction Of Supramolecular And Coordination Compounds From Pyridyl Bis-Urea Macrocycles, Bozumeh Som

Theses and Dissertations

The self-assembly of macrocyclic molecules in solution and in the solid state modulates and in many cases enhances their properties for applications in sensing, catalysis and optoelectronics. The self-assembled structures are typically organized by non-covalent interactions such as hydrogen bonding, π-π stacking and dipole-dipole interactions. Our group has focused on the design and synthesis of bis-urea macrocycles that can self-assemble into solid cylinders or tubular structures affording crystalline materials. These macrocycles consist of two urea groups and two rigid C-shaped spacers. Easy functionalization of this system enables access to bis-urea macrocycle structures that could serve as molecular reactors, coordinating ligands …

Design, Synthesis, Characterization, And Applications Of Matrix Free Polymer Nanocomposites, Yucheng Huang

Theses and Dissertations

This dissertation focuses on the design, synthesis, characterization and application of matrix free polymer nanocomposites. Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to synthesize block copolymers and polymer grafted silica nanoparticles with precise control over architectures.

In the first chapter, thermoplastic elastomer (TPE) grafted nanoparticles were prepared by grafting block copolymer poly(styrene-block-(n-butyl acrylate)) onto silica nanoparticles (NPs) (~15nm) via surface initiated RAFT polymerization. The effects of polymer chain length and graft density on the mechanical properties were investigated using films made solely from the grafted NPs. The ultimate tensile stress and elastic modulus increased with the increase of PS …

Synthesis And Reactivity Of Carborane Backbone Pincer Complexes, Bennett J. Eleazer

Theses and Dissertations

In organometallic chemistry, boron-centered ligand systems represent a powerful synthetic strategy for the promotion of a variety of catalytic transformations. These ligands offer a versatile array of bonding motifs, which can function as borane, boratrane, boryl, borate, or borylenes type ligands, and are likely the strongest σ-donors in the anionic series of ligands based on boron, carbon, nitrogen, and oxygen. Carboranes, which are icosahedral boron clusters of the type C2B10H12, offer unique potential as metal ligands, such as their bonding to exohedral metal centers being dominated by two-center-two-electron σ-bond interactions, their three-dimensional cluster structure providing considerable steric shielding to a …

Designed Polymer Brush Interfaces For Plutonium Separations And Polyethylene Nanocomposites, Julia G. Pribyl

Theses and Dissertations

Modification of surfaces with polymer brushes has become an important area of research for developing materials with a variety of advanced properties. Flat or continuous surfaces modified with polymer brushes can serve as surfaces where chemical reactions or separations take place, and discrete nanoparticles covered in a polymer brush can disperse within a miscible surrounding polymer, generating a composite which retains the processability of the polymer but becomes endowed with the properties of the filler as well. Presented herein are new synthetic approaches to modify both continuous surfaces as well as discrete particles with polymer brushes for complex applications. In …

Synthesis And Characterization Of Polydiene-Grafted Nanoparticles, Zaid Mohammed Abbas Alajeeli

Theses and Dissertations

This dissertation presents the design, synthesis, and characterization of polydiene grafted nanoparticles as a way to tailor nanocomposite interfaces and properties via interface design. The polymerization of dienes was done via reversible addition fragmentation chain transfer (RAFT) polymerization. The grafting of polymer chains on the surface of silica nanoparticles can be controlled through the molecular design of the RAFT agents attached to the nanoparticles surface. The properties of the nanocomposites largely depended on the interface between the particles and the polymer matrix. In the first part of this work, the polymerization of diene monomers was done on 15 nm diameter …

Development Of A High-Resolution Spatial Heterodyne Libs Spectrometer, Kevin A. Dudley

Theses and Dissertations

Laser-Induced Breakdown Spectroscopy (LIBS) is an atomic emission technique that uses a pulse laser to ablate a sample and form a plasma. Atomic emissions from the plasma provide unique elemental characteristics regarding the composition of the sample. The technique produces valuable qualitative results, but the accuracy of quantitative analyses is hindered by spectral line broadening mechanisms and laser pulse reproducibility, among other factors. The Spatial Heterodyne Spectrometer (SHS) is a high-resolution spectrometer with very high light throughput, and its use to LIBS is currently limited to two peer-reviewed publications. In the following work a high resolution SHS is developed and …

Hydrogen-Bonding-Directed Ordered Assembly Of Carboxylated Poly(3-Alkylthiophene)S, David W. Bilger, Jose A. Figueroa, Neil D. Redeker, Amrita Sarkar, Morgan Stefik, Shanjuu Zhang

Faculty Publications

Hydrogen-bonding-induced ordered assembly of poly(3-alkylthiophene)s derivatives bearing carboxylic acid groups has been investigated from diluted and concentrated solutions to solid films using ultraviolet–visible absorption spectroscopy, polarized optical microscopy, and four-point probe conductivity measurements. In dilute solutions, the polymer undergoes a spontaneous structural transition from disordered coil-like to ordered rodlike conformations, which is evidenced by time-dependent chromism. Many factors such as alkyl-chain length, types of solvents, and temperature are studied to understand the assembly behavior. Transition kinetics of the assembly process reveals a universal second-order rate law, indicating an intermolecular origin due to hydrogen bonding. When more concentrated, hydrogen bonding drives …

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 …

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 …

Rapid Reversible Borane To Boryl Hydride Exchange By Metal Shuttling On The Carborane Cluster Surface, Bennett J. Eleazer, Mark D. Smith, Alexey A. Popov, Dmitry V. Peryshkov

Faculty Publications

In this work, we introduce a novel concept of a borane group vicinal to a metal boryl bond acting as a supporting hemilabile ligand in exohedrally metalated three-dimensional carborane clusters. The (POBOP)Ru(Cl)(PPh3) pincer complex (POBOP ¼ 1,7-OP(i-Pr)2-m-2-carboranyl) features extreme distortion of the two-center-two-electron Ru–B bond due to the presence of a strong three-centertwo-electron B–H/Ru vicinal interaction. Replacement of the chloride ligand with a hydride afforded the (POBOP)Ru(H)(PPh3) pincer complex, which possesses B–Ru, B–H/Ru, and Ru–H bonds. This complex was found to exhibit a rapid exchange between hydrogen atoms of the borane and the terminal hydride through metal center shuttling between …

A Perspective On How To Improve Undergraduate Research Education In The Physical Sciences At Usc, Michael Caleb Bagley

Senior Theses

My years at the University of South Carolina have been some of the most challenging and edifying periods of my life. I have been blessed by having a great professional and chemistry mentor in Dr. John L. Ferry who has helped me engage in scientific research in a meaningful way. As I watched other chemistry students, in particular, struggle with understanding what research really was and even how to understand the results and methodologies of it I felt that this was a huge issue that could be rather simply fixed. I have been privileged to apply for and receive a …

Characterization Of Sufs And Sufe Of Suf Pathway For Fe-S Cluster Assembly In Escherichia Coli, Guangchao Dong

Theses and Dissertations

Fe-S clusters are one major type of the sulfur-containing cofactors, which conduct essential functions in organisms. The Suf pathway is one of the three main pathways for the biosynthesis of Fe-S clusters. In E. coli, the Suf pathway is utilized under iron limitation and oxidative stress. This ability is important for pathogens to survive. Also, the Suf pathway is found to be exclusive in bacteria, so it is a good target for novel antibiotic design. SufS is a cysteine desulfurase in the Suf pathway to extract sulfur from L-cysteine. It needs the enhancement of SufE. To better understand the catalytic …

Advances In Chemistry, Part I: Noise, Calibration, And Educational Advances In Analytical Chemistry. Part Ii: Safety Oversight In Chemical Journals, Lauren E. Grabowski

Theses and Dissertations

Part I:

The accuracy and precision of the results of any chemical analysis depends on the calibration graph and its associated systematic and random errors. Least squares regression generally treats all data with equal weights. A weighted least-squares fit is an improvement but requires knowledge of the imprecision in each point of the calibration graph. The imprecision is not easy to estimate with high confidence because of the large number of replicates needed.

The imprecision depends on the types and magnitudes of the sources of noise. We characterized the noise sources in ICP-OES and UV/Vis and developed a model that …

Antimicrobial Biomaterials And Sustainable Polymers From Renewable Biomass, Mitra Shiran Ganewatta

Theses and Dissertations

In this dissertation, development of antimicrobial biomaterials and sustainable polymers from renewable biomass is described. In Chapter 1, an overview and recent development about sustainable polymers from renewable biomass, antimicrobial biomaterials and polymerization methods are given. Afterwards, the major research objectives of this doctoral research work are described.

Innovative cationic polymers containing pine resin sourced abietic acid is discussed in Chapter 2. The preparation of cationic compounds is conversed via a combination of Diels-Alder, catalytic esterification, quaternization and subsequent decoration of polycaprolactone that was prepared via ring-opening polymerization (ROP). Furthermore, the antimicrobial activity against a range of bacteria, biocompatibility with …

Shaping Metallic Nanoparticles Toward Integrated Plasmonics And Catalysis, Qingfeng Zhang

Theses and Dissertations

Noble metal nanoparticles have been of tremendous interest because of their intriguing size- and shape-dependent plasmonic and catalytic properties. The combination of tunable plasmon resonances with superior catalytic activities on the same nanoparticle, however, has long been challenging because plasmonics and catalysis require nanoparticles in two drastically different size regimes. Tunable plasmon resonances is a unique feature of sub-wavelength metallic nanoparticles, whereas heterogeneous catalysis requires the use of sub-5 nm nanoparticles as the catalysts. In this dissertation, I firstly found a unique way to bridge this size gap between nanoplasmonics and nanocatalysis. I demonstrated that desired plasmonic and catalytic properties …

Emerging Antimicrobial Research Against Superbugs: Perspectives From A Polymer Laboratory, Mitra S. Ganewatta, Md Anisur Rahman, Chuanbing Tang

Journal of the South Carolina Academy of Science

Infectious diseases caused by drug-resistant microorganisms have become a major contributor for human morbidity and mortality. To overcome such threats, we have developed various antimicrobial agents using natural product derivatives and metallopolymers. Abundant biomass such as resin acids can be utilized to prepare cationic polymers for inhibiting a variety of bacteria. These polymers have been used in solution as well as surfaces as antimicrobial materials with low cytotoxicity. In addition, a class of charged metallopolymers have been developed to kill superbugs such as MRSA.

Table Of Contents

Journal of the South Carolina Academy of Science

No abstract provided.

Using Polymerization, Glass Structure, And Quasicrystalline Theory To Produce High Level Radioactive Borosilicate Glass Remotely: A 20+ Year Legacy, Carol M. Jantzen

Journal of the South Carolina Academy of Science

Vitrification is currently the most widely used technology for the treatment of high level radioactive wastes (HLW) throughout the world. Most of the nations that have generated HLW are immobilizing in borosilicate glass. One of the primary reasons that glass has become the most widely used immobilization media is the relative simplicity of the vitrification process, e.g. melt a highly variable waste with some glass forming additives such as SiO₂ and B₂O₃ in the form of a premelted frit and pour the molten mixture into a stainless steel canister. Seal the canister before moisture can enter …

Antitumor Activity Of Selected Derivatives Of Pyrazole- Benzenesulfonamides From Dilithiated C(Α), N-Phenylhydrazones And Lithiated Methyl 2-(Aminosulfonyl)Benzoate, N. Dwight Camper [Deceased], James M. Gum, Darby E. Lyles, William T. Pennington, Charles F. Beam, Clyde R. Metz

Journal of the South Carolina Academy of Science

Several pyrazole-benzenesulfonamides were subjected to biological evaluation involving tumor formation on potato discs caused by Agrobacterium tumefaciens. This assay led to some excellent and promising initial results with three of the pyrazole compounds showing increased tumor inhibition when compared to a recognized standard, camptothecin. The select pyrazole-benzenesulfonamides were prepared by condensation-cyclization of several dilithiated C(α),N-phenylhydrazones with lithiated methyl 2-aminosulfonyl-benzoate.

Differential Response Of Coral Symbiotic Dinoflagellates To Bacterial Toxins That Produce Bleaching In Stony Corals, Diego L. Gil-Agudelo, Yael Ban-Haim, Eugene Rosenberg, Garriet W. Smith

Journal of the South Carolina Academy of Science

Bleaching of corals and other organisms with symbiotic zooxanthellae is a worldwide phenomenon with increasing importance due to global warming scenarios. Bleaching has been historically related to changes in the environment, especially water temperature increase, that stress corals and provoke the release of zooxanthellae. The discovery of Vibrio shilonii, a bacterium causing bleaching under thermal stress in corals of the Mediterranean Sea has changed our thinking about the cause (or explanation) for bleaching of corals worldwide. During this study, we evaluated the effect of a proline rich toxin, extracted from Vibrio shilonii, on zooxanthellae obtained from: Oculina patagonica from the …

Where Do New Materials Come From? Neither The Stork Nor The Birds And The Bees! In Search Of The Next “First Material”, Gregory Morrison, Dileka Abeysinghe, Justin B. Felder, Shani Egodawatte, Timothy Ferreira, Hans Conrad Zur Loye

Journal of the South Carolina Academy of Science

Materials discovery and optimization has driven the rapid technological advancements that have been observed in our lifetimes. For this advancement to continue, solid-state chemists must continue to develop new materials. Where do these new materials come from? In this review, we discuss the approaches used by the zur Loye group to discover the next “First Material”, a new material exhibiting a desired or not previously observed property that can be optimized for use in the technologies of tomorrow. Specifically, we discuss several crystal growth techniques that we have used with great success to synthesize new materials: the flux growth method, …

Hierarchical Corannulene-Based Materials: Energy Transfer And Solid-State Photophysics, Allison M. Rice, W. Brett Fellows, Ekaterina A. Dolgopolova, Andrew B. Greytak, Aaron K. Vannucci, Mark D. Smith, Stavros G. Karakalos, Jeanette A. Krause, Stanislav M. Avdoshenko, Alexey A. Popov, Natalia B. Shustova Prof. Dr.

Faculty Publications

We report the first example of a donor–acceptor corannulene-containing hybrid material with rapid ligand-to-ligand energy transfer (ET). Additionally, we provide the first time-resolved photoluminescence (PL) data for any corannulene-based compounds in the solid state. Comprehensive analysis of PL data in combination with theoretical calculations of donor–acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand-to-ligand ET rate calculated using two models is comparable with that observed in fullerene-containing materials, which are generally considered for molecular electronics development. Thus, the presented studies not only demonstrate the possibility of merging the intrinsic properties of π-bowls, …

The Development Of Novel Hybridized Hyaluronic Acid Biomaterials For Applications In Tissue Engineering And Controlled Drug Delivery, Panita Maturavongsadit

Theses and Dissertations

This thesis is focused on the development of novel hybridized biomaterials for applications in tissue engineering and controlled drug delivery. Two types of materials used in my research are biopolymers and nanomaterials. Hyaluronic acid (HA), a natural polymer commonly found in extracellular matrix (ECM), was the primary polymer used in my research due to biocompatibility, biodegradability and the ease of manipulation to offer a wide range of physical and mechanical properties. Meanwhile, the nanomaterials, including Tobacco mosaic virus (TMV), gold nanorods and graphene, provide attractive properties, such as a nanoscale topography, biochemistry, high surface area, and special chemical and electrical …