Materials Chemistry Commons^™

Catalytic Innovation For Sustainable Styrene Production: Green Chemistry Strategies Utilizing Octahedral Ruthenium (Ii) Complexes Supported By A Single Bipyridine Ligand, Kennedy G. Musso, Brandon Quillian, Clifford Padgett, Jose Jimenez

College of Graduate Studies: Theses & Dissertations

This study investigates: 1) the synthesis and reactivity of the mono- substituted systems, [κ²-(t-bipy)Ru(NCMe)2(Ph)(PR3)][BArF'] supported by different ancillary ligands PR3 = (P(OCH3)3 and P(CH3)3) and a single bidentate ligand, 4,4′-di-tert-butyl-2,2′-bipyridine (t-bipy), and 2) UV/heat formation of di-PR3 and tri-PR3 systems supported by a single bidentate ligand to better understand the mechanism of styrene production. Utilizing [(η6-p-cymene)RuI(µ-I)]2 (1), the complexes (η6-p-cymene)RuI2(P(OCH3)3) (2) and (η6-p-cymene)RuI2(P(CH3)3) (3) were synthesized and phenylated to produce (η6-p-cymene)RuI(Ph)(PR3) (6; PR3 = P(OCH3)3 and 7; PR3 = P(CH3)3). Complex 4, (η6-p-cymene)RuCl2(P(CH3)3), was also synthesized and phenylated to produce (η6-p-cymene)RuClPh(P(CH3)3) (5) to understand the impact of chloride versus iodine …

Characterization And Optimization Of Sand And Tung Oil-Based Resins For Binder-Jet 3d Printing, Daniel I. Ajiola

College of Graduate Studies: Theses & Dissertations

Binder-jet 3D printing as a transformative technology in additive manufacturing, offers the ability to fabricate complex structures with diverse materials. This thesis investigates the use of a sustainable tung oil-based resin to create composites, exploring the potential for an eco-friendly alternative to synthetic binders.

The aim of this research is to develop and characterize a bio-based resin formulation, using tung oil as the primary binder, for application in binder-jet 3D printing with sand as the reinforcement. The resin formulation was prepared by combining tung oil, n-butyl methacrylate, divinylbenzene, and di-tert-butyl peroxide in precise proportions, ensuring a balanced mixture that supports …

Synthesis And Characterization Of A Biobased Polymer From Tung Oil And Pine Rosin & Characterization Of Polyhydroxybutyrate., Arijanet P. Osumah

College of Graduate Studies: Theses & Dissertations

This thesis presents two independents but thematically aligned research projects focused on the development and evaluation of sustainable polymers. The first involves the synthesis and characterization of a biobased polymer derived from tung oil and pine rosin. Tung oil, which is a triglyceride was chemically modified to produce tung oil diglyceride (TDG), which subsequently reacted with abietic acid-rich pine rosin to yield tung oil abietate (TOA), a biobased monomer. The TOA monomer was polymerized with butyl methacrylate (BMA) and divinylbenzene (DVB) using di-tert-butyl peroxide (DTBP) as a thermal initiator. The resulting polymer was thoroughly characterized using Fourier transform infrared spectroscopy …

Concentration Effects Of Ytterbium(Iii) Ions On The Physical, Structural, Thermal, And Optical Properties Of Barium Phosphate Glasses, Richard Amesimenu

College of Graduate Studies: Theses & Dissertations

Ytterbium(III)-doped glasses are widely known for their application in near-infrared (NIR) lasers and nowadays attract attention for solar spectral conversion in photovoltaic cells. In this study, the effects of ytterbium(III) concentration on the physical, structural, optical, and thermal characteristics of Yb-doped phosphate glasses were investigated. The glasses were synthesized using the melt-quenching technique with nominal compositions of 50P₂O₅:(50 – xBaO):xYb₂O₃ (x = 0, 0.5, 1.0, 2.0, 3.0 and 4 mol%). The properties were then examined by density and related parameters, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform-infrared …

A Comparison Of Tung Oil Resin Reinforcements Using Fibrous Proteins And Peptides For Biological And Materials Applications, Parker L. Williams

College of Graduate Studies: Theses & Dissertations

In this study a tung oil based thermoset was reinforced with collagen and fibroin, and the resulting composites were analyzed for their physical properties. Tung tree seed oil is a great candidate for biobased polymer production because its triglycerides are primarily made of alpha eleostearic acid, a fatty acid with three conjugated carbon-carbon double bonds. These double bonds allow for mechanically strong crosslinking in the polymer. It has been observed that polymerized tung oil forms a gel. This issue has been addressed using divinylbenzene (DVB) and n-butyl methacrylate (BMA) as co-monomers. Similar bio-based polymers have been studied and tend to …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Characterization Of Functionalized Carbon Nanotubes And Polystyrene/Cnt Composites Prepared With Microwave-Induced Polymerization, Allen Hulette

College of Graduate Studies: Theses & Dissertations

The use of carbon nanotubes in polymer composites can increase the mechanical properties of the resulting product. Carbon nanotubes are known to have chemical interactions that make them attracted to one another and fall out of solution. To reduce this agglomeration and disperse the mechanical properties throughout the composite, functional groups are covalently added to the carbon nanotubes. Another known property of carbon nanotubes is their ability to absorb microwaves and convert it into other forms of energy. This research investigates the effects of carbon nanotube absorption of microwaves and initiation of styrene monomer polymerization. Grignard reactions are used to …

Molybdenum Oxide/Antimony Nanobelts Embedded In Asymmetric Membranes For Use As High-Capacity Lithium/Sodium-Ion Battery Anodes, Logan Williams

College of Graduate Studies: Theses & Dissertations

Lithium-ion batteries (LIB) are a key aspect of our daily lives, from smartphones to electric vehicles. Commercially available LIB use graphite anodes due to their reliability and safety. Graphite anodes present one key disadvantage: a relatively low theoretical capacity of 372 mAh g-1. It is of great importance that new research focuses on high-capacity anode materials to further our sustainability and usage of LIB. While increasing the performance of LIB is of great interest, developing alternative energy storage devices is gaining attention in academia and industry R&D. Sodium has become a topic of interest in recent years due to sodium’s …

Investigation Of Intramolecular And Intermolecular Aza-Michael Reactions, Nadia Z. Singleton

College of Graduate Studies: Theses & Dissertations

The hydroamination of dimaleimides with diamines has been accomplished to access novel polymers. Various dimaleamides and dimaleimides were synthesized from commercially available diamines and maleic anhydride. The resulting dimaleamides were then ring-closed to their respective dimaleimides either directly in the presence of acid or via the synthesis of mixed amide-esters which then ring close in the presence of acid under heat. Hydroamination of the dimaleimides with piperazine was accomplished in bulk at room temperature. The reaction is spontaneous thus leading to the formation of polyimides with high functional group conversion within minutes. The kinetics of the maleamides and maleimides was …

The Effects Of Nacl On The Triple Helix Structure Of Collagen And The Reinforcement Of Tung Oil-Based Polymers With Collagen Peptides, Christopher Dzorkpata

College of Graduate Studies: Theses & Dissertations

In this research, a collagen-reinforced bio-composite from tung oil was prepared using free radical initiation and thermal polymerization, leading to polyolefinic tung oil-based matrix. Two peptides (long and short) were synthesized and their secondary features were analyzed using circular dichroism spectroscopy. After this analysis, the long peptide exhibited more triple helix characteristics as compared to the short peptide. The full protein will ultimately have a better interaction with the tung oil, was used in the synthesis of the collagen-reinforced bio-composite. The presence of NaCl in the triple helix and its overall effect on the thermal and mechanical properties of the …

Synthesis Of N-Heterocyclic Molecules And Their Applicability Towards Ion Sensing: Polymeric Chemosensors, Aikohi M. Ugboya

College of Graduate Studies: Theses & Dissertations

Critical to biological and environmental processes are anions because often times their relative concentration in our body can be an indicator of one’s well-being. Therefore, highly sensitive and cost-efficient methods for ions recognition is necessary for human health. In recent times, polymeric chemosensors have become a vital tool for sensing ions because of its higher sensitivity and good mechanical properties compared to their monomeric counterparts. These sensors are designed to produce a measurable response in the presence of a targeted ion such as an electrochemical or optical signal. The unique structure and the photophysical properties of the 1,2,3-triazole core coupled …

Asymmetric Membranes For High Capacity Lithium-Ion Battery Electrodes, Ian Byrd

College of Graduate Studies: Theses & Dissertations

Lithium-Ion Batteries (LIBs) have broad applications such as portable electronic devices, electric vehicles, and for green energy storage from intermittent sources. Current LIBs are limited by their low capacity materials at both the anode and cathode. At the anode, graphite suffers from a low capacity of only 372 mAh g^-1. The most commonly used cathode material is LiCoO₂ which has a meager capacity of 140 mAh g^-1. Thereby the broader applications of LIBs are limited due to these low capacities. It is imperative to develop higher capacity materials to further improve the performance of LIBs. …

Synthesis Of Multifunctional Polyacrylates And A Binding Group To Hemoglobin For The Treatment Of Traumatic Brain Injuries, Marina Michaud

Honors College Theses

Hemoglobin based oxygen carriers (HBOCs) hold promise as an effective emergency treatment of severe traumatic brain injuries (TBI). In the latest generation of HBOCs, polynitroxyl-pegylated hemoglobin (PNPH), cell-free hemoglobin is modified with TEMPO and PEG which reduce the toxicities associated with earlier generations of HBOCs. In our efforts to optimize the economic and therapeutic impacts of PNPH’s we have synthesized polydimethylaminoethyl methacrylate (poly-DMAEMA) under controlled living conditions via reverse addition-fragmentation chain transfer (RAFT) polymerization. The poly-DMAEMA was then successfully functionalized via quaternization of its NMe₂ groups using chloroacetate derivatives of the TEMPO and PEG. This process was quantitative and …

Α-Eleostearic Acid Extraction By Saponification Of Tung Oil And Its Subsequent Polymerization, Amanda Murawski

College of Graduate Studies: Theses & Dissertations

The goal of environmentally sound research is to provide alternatives that are more sustainable and renewable, such as vegetable oil-based polymers, than the current petroleum-based products. Vegetable oil-based polymers have received a lot of attention recently due their multifaceted properties, which are simply achieved by adjusting the monomer or resin composition. The carbon-carbon double bonds in unsaturated oils are ideal reactive sites for the free radical or cationic polymerizations. Most vegetable oils must be modified before polymerization due to the low reactivity of their non-conjugated fatty acid chains. Tung oil (TO) contains ~83% of a triply conjugated fatty acid ( …

Tempo-Containing Romp Polymers As A Component For Treatment Of Traumatic Brain Injuries, Cameron H. Feriante

Honors College Theses

During a traumatic brain injury (TBI) sustained in combination with hemorrhagic shock the brain undergoes anoxic conditions resulting from swelling and blood loss. Traditional intravenous solutions are used to replace blood volume, but are unable to replace the blood’s oxygen carrying capacity. A proposed treatment based on isotonic solutions containing hemoglobin-based oxygen carriers (HBOC’s) which were intended to provide readily available oxygen was developed. However, cell-free hemoglobin was shown to have excessive oxidative potential. Polynitroxylated Pegylated Hemoglobin (PNPH) was developed to address this shortcoming. During PNPH synthesis a combination of polyethylene glycol (PEG) and (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), is bound to the …

Investigations Of Synthetic Fuels: S8 And Sasol Ipk To Determine The Possibility Of Alternate Fuels In The Aerospace Industry, Scott M. Dyke

GS4 Student Scholars Symposium

Investigations of Synthetic Fuels: S8 and Sasol IPK to Determine the Possibility of Operation as Alternate Fuels in the Aerospace Industry

Name: Scott Dyke

Co-Authors: Martin Muinos, Julia Heimberger, Dr. Valentin Soloiu,

An ever-growing society that becomes more and more dependent on a finite energy source will eventually exceed its supply. Fossil fuel quantities are continuously decreasing and new solutions are needed. According to the United States Department of Transportation, over 10 billion gallons of airline fuels have been consumed in each of the past 15 years with some years over 13 billion gallons. In the meantime, fuel costs have …

Electrospun Titanium Dioxide And Silicon Composite Nanofibers For Advanced Lithium Ion Batteries, Kathleen Mccormac

College of Graduate Studies: Theses & Dissertations

A unique electrospinning method was implemented to fabricate composite nanofibers for lithium ion battery applications. The composite nanofibers were made of amorphous carbon, rutile phase TiO₂, and cubic phase Si nanoparticles. Sulfur was utilized as a template to form void structures within the TiO₂ nanofiber matrix. This provides the desired space for the Si expansion during the lithiation process. Phase, structure, composition, and morphology of the nanofibers were characterized using Raman spectroscopy, SEM, EDS, TGA, and powder XRD. Carbonized TiO₂ nanofibers showed a low but stable specific capacity. Si Nanoparticles demonstrated an initially high but fast …