Digital Commons Network^™

Synthesis Of Block Copolymer Additives For Examining Phase Morphology And Improving Mechanical Properties Of Thermoplastics Elastomers., Bishal Upadhyay

Masters Theses

Polystyrene-block-poly(1,4-butaidene)-block-polystyrene (PS-PB-PS) triblock copolymers are one of the most widely studied thermoplastic elastomers (TPEs) due to their ease of synthesis, non-polar nature, and commercial applicability. Like many block copolymers, incompatibility between PS and PB causes these TPEs to undergo microphase segregation. Many studies have examined the mechanical properties of blends of TPEs and PS homopolymer additives. However, there have been few studies focused on understanding the morphology and mechanical properties of blends of TPEs and copolymer additives with different architectures. Herein, I describe the synthesis of linear and graft copolymer additives based on the random copolymers poly(methyl methacrylate-random-cyclohexyl methacrylate) (PrC). …

The Influence Of Ion-Ion Correlations On Conductivity In Concentrated Ionic Systems, Md Dipu Ahmed

Masters Theses

This study delves into the fascinating realm of concentrated ionic systems, such as ionic liquids, superionic materials, organic ionic plastic crystals, and polyelectrolytes, which hold immense potential for energy storage applications. The focus is on understanding the intricate role of ionic correlations in shaping their ionic conductivity behavior. These correlations can either boost or impede conductivity, yet their underlying mechanisms remain elusive. Through extensive investigation of various materials, including ionic liquids with differing anionic masses, pure organic ionic plastic crystals, and doped systems, this research employs advanced techniques like dielectric spectroscopy and innovative momentum conservation models to quantify these correlations. …

Machine Learning Modeling Of Polymer Coating Formulations: Benchmark Of Feature Representation Schemes, Nelson I. Evbarunegbe

Masters Theses

Polymer coatings offer a wide range of benefits across various industries, playing a crucial role in product protection and extension of shelf life. However, formulating them can be a non-trivial task given the multitude of variables and factors involved in the production process, rendering it a complex, high-dimensional problem. To tackle this problem, machine learning (ML) has emerged as a promising tool, showing considerable potential in enhancing various polymer and chemistry-based applications, particularly those dealing with high dimensional complexities.

Our research aims to develop a physics-guided ML approach to facilitate the formulations of polymer coatings. As the first step, this …

Expression And Purification Of Polyketide Synthase Domains To Investigate Protein-Protein Interactions In Polyketide Biosynthetic Pathways, Mujeeb Adeyinka Wakeel

Masters Theses

Polyketide synthases (PKSs) are multienzyme proteins catalyzing the production of the polyketide class of natural products with vast structural diversity. Type II PKSs catalyze polyketide biosynthesis using discrete (standalone) enzymes (domains), while type I PKSs use covalently linked enzymes arranged in a module to catalyze polyketide production. It is hypothesized that type II PKSs are the precursors to type I PKSs, proposing that the genes encoding individual discrete enzymes in type II PKSs fused to give the multienzyme modules of type I PKSs. We reasoned that the intramolecular-like reactions occurring in type I PKS modules might be a driving force …

Redox-Active Polymerization Catalysts And Their Applications, Nicholas M. Shawver

Masters Theses

Traditional catalyst systems are reliable means to produce polymers with well-defined architectures and thermomechanical properties; however, they are often limited by a narrow monomer scope and their ability access few, if any, advanced polymer architectures. To address this limitation, a new class of catalysts have recently emerged that feature redox-active moieties that may access advanced architectures through catalyst electronic modulation that arises from redox events occurring on the ligand scaffold or at the active metal center itself. For example, researchers have explored the ability of redox-active catalysts to impart “on-off” kinetic control during ring-opening polymerizations and their ability to access …

Copper-Indazolate Nanojars: Synthesis And Characterization, Nicholas Alexander Rudell

Masters Theses

The field of synthetic supramolecular chemistry has exploded since the first syntheses of crown ethers by Charles Pedersen in the 1960s, leading to further development in the area of macrocycles and incorporation into a vast array of metal-organic structures. Supramolecular chemistry came to the forefront of science with the 1987 Nobel Prize in Chemistry, awarded jointly to Donald J. Cram, Jean-Marie Lehn, and Charles Pedersen “for their development and use of molecules with structure-specific interactions of high selectivity.”

Nanojars are supramolecular metal-organic complexes with a high affinity for hydrophilic anions and can efficiently transfer such anions from water into organic …

Impact Of Cover Crop Species Diversity On Soil Nutrient Availability And Crop Productivity, Amanda Kramer

Masters Theses

Cover crops provide multiple environmental benefits that improve both soil and water quality; however, farmers only utilize them on approximately 5% of harvested U.S. cropland. Low adoption rates are attributed to yield impact concerns, seed and planting costs, and lack of advocacy. This study, which began in October 2019, assessed the effects of nitrogen rate and cover crop diversity on weed biomass, soil coverage, in-situ residue decomposition, soil nitrogen and phosphorus availability, and cash crop yield to better understand the costs and benefits of cover crop adoption at two locations in Tennessee (Milan and Spring Hill). Treatments were replicated 4 …

Understanding The Polymerization Of Ethyl Cyanoacrylate In The Superglue Fuming Of Latent Prints To Optimize Print Retrieval, Leondra Shawntae Lawson

Masters Theses

The cyanoacrylate fuming method (CFM) is a widespread process used in forensics to make latent prints visible for detection, acquisition, and analysis. CFM is governed by the reaction of ethyl cyanoacrylate (ECA) with biological components in fingerprints, which serve as initiators for this anionic polymerization. CFM is not a well-controlled polymerization and there are different outcomes that may result from lower temperature, one of which fits the generalization of creating more ion-pair initiators. Another effect could be minimizing termination through suppressing side reactions. Alternatively, when paired with humidity, lower temperatures may cause surface condensation, decreasing the quality of the print. …

Development And Study Of Small Database For The Activation Of Nitrous Oxide Towards Formation Of Iron(Iv)-Oxo Species, Tobias Barthalomew Robertson

Masters Theses

Nitrous oxide (N₂O) can undergo an oxygen atom transfer (OAT) reaction resulting in inert nitrogen gas (N₂O) while transferring an oxygen atom to a molecular complex or material. This process is of catalytic importance since this OAT reaction can be leveraged to form iron(IV)-oxo sites, which are known to be catalytic intermediates. Here, an investigation of the ligand field effects on primarily iron(II) complexes for the formation of iron(IV)-oxo sites with nitrous oxide as the oxidant is reported. An initial database of sixty-four molecular complexes with ligand environments varying in field strength and coordination geometry was …