Chemistry Commons^™

A Novel Method For Confirming The Presence Of Volatile Reduced Sulfide Compounds Via Inductively Coupled Plasma-Optical Emission Spectroscopy, Krystal Lynne Parker

Master's Theses

Millions of dollars in destruction in the past decade have resulted from the use of Chinese drywall in homes. There are also potential health hazards related to this corrosive material. As such, it is important to find a way to identify Chinese drywall. Drywall can be tested for certain markers, such as strontium, sulfur, and carbonates to identify it as corrosive Chinese drywall. The laboratory preparation and analysis should be efficient and cost effective. The methods previously used, such as an X-ray fluorescence gun have had issues with getting a proper reading due to the layers of other materials found …

Mineralogical Transformation And Electrochemical Nature Of Magnesium-Rich Primers During Natural Weathering, Shashi S. Pathak, Michael D. Blanton, Sharathkumar K. Mendon, James W. Rawlins

Faculty Publications

Magnesium-rich primers (MgRP) have generated great interest as a promising alternative to chromium-based primers for the protection of aluminum substrates but their performance during exterior exposure has not been well documented. This paper focuses on the evaluation of MgRP during natural weathering to gain insight into its mineralogical phase transformation and electrochemical nature. Control studies were conducted on Mg and AA2024-T3 coupons. The results indicate that Mg particles in MgRP transform into a variety of hydroxide, carbonate, and hydroxy carbonates. During natural weathering, CO₂ inhibited the dissolution of both Mg and AA2024-T3 as a result of protective carbonate layer …

Raft Polymerization Of Sulfonamide-Containing Methacrylamides, Michael B. Sims

Honors Theses

Targeted delivery of cancer therapeutics offers an exciting new opportunity for utilization of controlled polymerization techniques. However, a major obstacle in achieving the desired therapeutic effect is facilitating endosomal release of active agents following endocytosis. Peptides and pH-responsive polymers have been utilized as a means of triggering endosomal release via phase transition-induced membrane disruption. Unfortunately, the fidelity by which the pKa of these polymers/peptides can be varied is limited, such that it reduces their versatility in altering the phase transition point to best match the endosomal pH of a particular cell-type. Herein, we report the controlled polymerization of library of …

Biogeochemistry Of Trace Elements In The Mixing Zone Of The Mississippi And Atchafalaya Rivers And Chemical Distributions As Affected By The Deepwater Horizon Blowout, Dongjoo Joung

Dissertations

Selected trace elements (TEs), dissolved organic carbon, and nutrients were studied in Louisiana Shelf waters including the Mississippi (MR) and Atchafalaya (AR) River plumes during periods of high, intermediate, and low river discharges. Seasonal variations in TEs were observed at low salinity, reflecting seasonal changes in the river water endmembers. Shelf surface water dissolved Mo, Cs, U, Ni, and Cu showed conservative behavior with minor scattering in some high salinity waters. Based on associated mixing experiments, nutrient and chlorophyll distributions, as well as surface-bottom concentration contrasts, the non-conservative behavior of TEs was variously related to colloidal flocculation (Fe, Cr), biological …

Study Of The Structure-Property Relationships That Determine The Effects Of Latexes And Starch Containing Latex Emulsions On The Performance Of The Barrier Coatings (Sub-Coat) For Paper, Joanna Marie Monfils

Master's Theses

The history of carbonless paper dates back to the 1940s. Before this, a carbon copy sheet was needed between sheets of paper to be able to produce one or more copies simultaneously during writing. The pressure from a pen or typewriter would help deposit the ink of the carbon paper onto the blank sheet of paper under the original written sheet to create a “carbon copy.” This method did however, have its disadvantages. Not only did it produce a limited number of copies, but it was also a messy process. So came the creative process of using microencapsulated dyes to …

Effects Of Varying The Cure Profiles Of An Epoxy-Amine System, Patrick W. Hollingsworth

Honors Theses

The cure of an epoxy prepolymer with an amine hardener induces stress in thermosetting systems. The extent of residual stresses in the cured epoxy-amine thermosets are dependent on several factors; one of which is the cure profile utilized. The effect of cure profile on cure induced stresses of an epoxy-amine thermoset was examined in the current study. A difunctional epoxide based on diglycidyl ether of bisphenol-A (DGEBA) and a tetrafunctional amine curative were used to conduct this study. Two cure profiles were selected to prepare samples of varying degrees of stress in the cured thermosets. The first was constant heating …

Uv Curable Coatings For Improved Gas Barrier Properties Of Poly(Ethylene Terephthalate), Ethem Kaya, Tara Smith, Lon J. Mathias

Faculty Publications

A new high-barrier coating based on methyl (alpha-hydroxymethyl)acrylate (MHMA) for poly(ethylene terephthalate) (PET) was developed along with the process for preform dipping and cure prior to blow molding into bottles. The UV curable coating gives excellent gas barrier improvement when coated onto PET biaxially oriented thin films. Blown bottle side walls from coated PET preforms also show 2-3 times improvement over uncoated side walls. The effect of photoinitiator concentration, initiator types, and temperature on photopolymerization kinetics of MHMA was investigated. Once the photoinitiator, lrgacure 819 (R), concentration became larger than 1 mol%, a decrease in rate of propagation was observed. …

An Insight Into Asymmetric Synthesis And Bioorganic Applications Of Novel Cα- Methyl-Lysine, - Proline, - Nipocotic Acid Analogues, Souvik Banerjee

Dissertations

Prochiral malonic diesters consisting of a quaternary carbon center have been successfully converted into a different set of tBoc-Fmoc-α2,2-methyllysine-OH analogues through chiral malonic half-ester intermediates achieved via enzymatic (Pig Liver Esterase, PLE) hydrolysis. The selection of chiral half-ester intermediates, which vary from 1 to 6 methylene units in the side chain, are achieved in high optical purity (92% - 97% ee) and in good yields (65% - 72%). The PLE hydrolysis of malonic diesters with a variety of side chain lengths observed to obey the Jones’s PLE model as evidenced from the stereochemical configurations of the resulting chiral half-esters. The …

Design And Synthesis Of Flexible And Functional Polybenzoxazine Thin Films, Austin David Baranek

Dissertations

Polybenzoxazines offer the unique ability to incorporate a variety of properties and functionality into a single polymer network through simple synthetic techniques. However, within benzoxazine materials exist certain drawbacks of which brittleness is the primary issue when exploring thin film applications. This brittleness leads to poor mechanical stability and would reduce the lifetime of any device sought after. It is, however, through the simplistic nature of the benzoxazine monomer synthesis that the mechanical stability could be addressed chemically, avoiding the complications of using rubber toughening agents or plasticizers. The monomer synthesis offers tailorability of both the phenol and amine to …

In Situ Quenching And Post-Polymerization Modification Of Telechelic Polyisobutylene, Todd Raymond Hartlage

Dissertations

Polyisobutylene (PIB) is a saturated hydrocarbon elastomer that can only be produced by cationic polymerization. The water-initiated, chain transfer controlled synthesis conducted on an industrial scale produces monofunctional PIB with mixed olefin end groups. Living cationic techniques produce mono- and di-functional telechelic PIB. In situ quenching is the process of adding functional molecules to the polymerization reactor after all monomer is consumed. These quencher species bond to the chain ends, installing their latent functionality onto the polymer chain. To date, all quenchers utilized have been soft π-nucleophiles.

In the first project, free thiols, both aromatic and aliphatic, are shown to …

Biophysical Understanding Of Novel Synthetic Amyloid-Β (Aβ) Prions In Alzheimer's Disease, Amit Kumar

Dissertations

Oligomers of amyloid-β (Aβ) peptide are the primary toxic agents that play a pivotal role in the pathogenesis of Alzheimer’s disease (AD). Oligomers are the intermediates formed during the Aβ aggregation process leading up to insoluble fibrils. It is important to know that oligomers can also be formed via pathways that do not lead to fibril formation. Such ‘off-pathway’ oligomers would have significantly longer half-lives than the ‘on-pathway’ ones, which may result in prolonged toxicity to neuronal cells. Furthermore, neither the mechanism of neurotoxicity nor the potential mechanisms of propagation and proliferation to neighboring cells are well understood. Moreover, recent …

Relation Between The Adsorption Behavior And Bulk Complexation In Oppositely Charged Polyelectrolyte-Surfactant Systems: Effect Of Polyelectrolyte Concentration, Molecular Weight, Charge Localization And Backbone Rigidity/Hydrophobicity, Vipul Suhas Padman

Dissertations

Due to a wide range of applications, much emphasis has been placed on understanding the physicochemical behavior of polyelectrolyte/surfactant complexes, both at air-water interface and in the bulk. However, the correlation between the adsorption behavior and complexation in the bulk is less explored. In this research, this correlation is investigated and its dependence on polyelectrolyte concentration, molecular weight, charge localization and backbone rigidity and hydrophobicity is studied. The polyelectrolyte concentration is normalized with respect to it critical overlap concentration in order to compare the polymer in same concentration regime. Different polyelectrolyte systems were used to analyze the polyelectrolyte structural effect: …

Synthesis And Characterization Of Polyisobutylene-Block-Polyamides As Novel Thermoplastic Elastomers, Lauren Renee Kucera

Dissertations

Academic research has focused on two main areas of the living carbocationic polymerization (LCP) of isobutylene (IB): (1) the in-depth study and understanding of mechanistic features of the polymerization, and (2) the utilization and manipulation of the unique aspects of PIB in order to produce practically useful polymeric materials. The research included in this dissertation focuses mainly on the latter objective. This work details three main areas of research: (1) the copolymerization of PIB and polyamides (PA) to form novel thermoplastic elastsomers (TPEs), (2) the mechanical, physical and thermal properties of the novel PIB-PA materials, and (3) the use of …

Direct Chain-End Functionalization Of Living Polyisobutylene With Phenoxyalkyl(Meth)Acrylates, Conor Patrick Roche

Master's Theses

This volume describes efforts toward the synthesis and employment of phenoxyalkyl (meth)acrylates, which were used to end-quench 1sobutylene polymers m1tiated from 2-chloro-2,4,4-tnmethylpentane (TMPCl), and 5-tert-butyl-1 ,3-d1(1-chlorol- methylethyl)benzene (bDCC), respectively, at -70 °C in 40/60 (v/v) hexane/methyl chlonde. The quencher/cham end molar rat10s typically ranged from 2.5-4, while the ratio of Lewis ac1d/cham end was vaned from approximately 3 5-6 In all cases, alkylation occurred exclusively at the para position of the quencher and no cham degradat10n was observed, even at high concentrations of TiC14 and long reaction times. Prellmmary qualitative studies mvolved the reaction of quenchers of varymg alkyl tether …

Synthesis Of Polyhedral Oligomeric Silsesquioxane (Poss) Functionalized Carbon Nanotubes For Improved Dispersion In Polyurethane Films, Xiaonan Kou

Dissertations

Carbon nanotube (CNT) polymer nanocomposites are promising advanced materials. These materials exhibit the advantages of traditional polymeric materials, such as being light weight and easy to process, combined with the potential to exhibit enhanced mechanical, thermal and electrical properties compared to pure polymers. To achieve substantial improvement of composite properties at low CNT loading, uniform dispersion of CNTs in the polymer matrix and strong CNT-polymer interfacial interaction are needed. However, it is difficult to achieve adequate dispersion and interfacial interactions due to the inert nature of CNTs. In this project, polyhedral oligomeric silsequioxane (POSS) will be used as a dispersing …

Nanoparticle Filled Polymeric Systems For Gas Barrier And Flame Retardant Properties, Yingji Wu

Dissertations

Polymer composite gas barrier and fire retardant properties were studied in this investigation. An increase in the gas barrier property was observed by adding silicate nanotubes or clay nanoparticles into polymeric systems. Oxygen permeability, diffusivity, solubility and water vapor permeability were determined for polyimide/silicate nanocomposites with 0 to 9.99% (vol/vol) filler loading. Both oxygen and water vapor permeability for the system gradually decreased when adding increasing amounts of nanofiller up to 4.50% (vol/vol) and increase again after that. The permeability decrease was caused by both the diffusivity and solubility coefficient changes, although diffusivity (the tortuous factor) is the main reason …

Relationships Between Cure Kinetics, Network Architecture, And Fluid Sensitivity In Glassy Epoxies, Katherine Lea Frank

Dissertations

Relationships between chemical structure, cure kinetics, network morphology and free volume have been correlated with fluid ingress for glassy epoxy network blends. Polymers synthesized from diglycidyl ether of bisphenol-A (DGEBA) and diglycidyl ether of bisphenol-F (DGEBF) were blended with varying amounts of triglycidyl-m-aminophenol (TGAP), tetraglycidyl-4,4-diaminodiphenylmethane (TGMP), napthylamine (NA), adamantylamine (AA), and aminopropylisobutyl polyhedral oliogmericsilsesquioxane (AI-POSS) and cured with 3,3’- and 4,4’- diaminodiphenylsulfone (DDS) to control fractional free volume, average hole size and morphology.

Varying curing profiles introduced morphological changes resulting in differences in network architectures. Epoxy with 10% NA had a smaller V_h (71 ų) …

Utilizing Polymer Topology In Peptide-Based Block Copolymers: Unique Aqueous Assembly And Responsive Behavior, Jacob Griffin Ray

Dissertations

This document details work in the area of amphiphilic polypeptide-based block copolymers that are able to self-assemble into well-defined nanostructures in aqueous solution. The main focus of this work is to understand the impacts of polymer topology on self-assembly behavior and response to external stimulus, particularly pH. Poly(L-lysine) and poly(L-glutamic acid) are two pH-responsive, hydrophilic polypeptides that possess the unique property of undergoing α-helix to random coil secondary structure transitions with pH, and this responsiveness can lead to global morphology changes such as changes in aggregate size or even morphology transitions. These polypeptides are synthesized via ring opening polymerization of …

Dynamic Bioactive Stimuli-Responsive Polymeric Surfaces, Heather Marie Pearson

Dissertations

This dissertation focuses on the design, synthesis, and development of antimicrobial and anticoagulant surfaces of polyethylene (PE), polypropylene (PP), and poly(tetrafluoroethylene) (PTFE) polymers. Aliphatic polymeric surfaces of PE and PP polymers functionalized using click chemistry reactions by the attachment of –COOH groups via microwave plasma reactions followed by functionalization with alkyne moieties. Azide containing ampicillin (AMP) was synthesized and subsequently clicked into the alkyne prepared PE and PP surfaces. Compared to non-functionalized PP and PE surfaces, the AMP clicked surfaces exhibited substantially enhanced antimicrobial activity against Staphylococcus aureus bacteria. To expand the biocompatibility of polymeric surface …

Biological And Biologically Inspired Polymers For Interface Modification, Lea Clayton Paslay

Dissertations

Naturally occurring macromolecules are produced for a specific function and have the selectivity to accomplish objectives with little waste in energy. The scientific community strives to develop smart, efficient molecules on an economical scale, thus lessons can be learned from nature and applied to cost effective synthetic systems. First, the mimicry of naturally occurring antimicrobial peptides (AMPs) will be described. AMPs show great potential as alternatives to conventional antibiotics as they can selectively bind and eliminate pathogenic bacteria without harming eukaryotic tissues. Aqueous reversible addition–fragmentation chain transfer (RAFT) polymerization was utilized to prepare primary and tertiary amine containing AMP polymer …

Investigations Toward Tunability Of Mechanical, Thermal, And Impact Properties Of Thiol-Ene Networks For Novel High Energy Absorbing Materials, Olivia Devon Mcnair

Dissertations

The UV polymerization of thiols with electron rich alkenes is a highly resourceful reaction that has been utilized by scientists within various disciplines to produce an even more versatile display of applications. This dissertation focuses on a newer application, thiol-ene network (TEN) materials for energy absorption devices. TEN networks display a host of positive polymer properties such as low stress, high optical clarity and uniformity, but they also suffer from unfavorable mechanical properties such as low toughness and elongation at break. The poor mechanical properties demonstrated by TENs prohibit them as choice materials for applications requiring thicker material forms, including …

Photopolymerization And Characterization Of Modified Thiol-Ene Networks, Bradley James Sparks

Dissertations

Photopolymerization provides a unique ability to control variables typically uncontrollable using traditional thermally initiated polymerization, thus leading to its use in a broad range of commercial operations. Many of the traditional photopolymers suffer from several setbacks, including oxygen inhibition, unwanted stress buildup which leads to bulk shrinkage, etc., which ultimately lead to diminished polymer performance. The photopolymerization of multifunctional thiols and alkenes has been shown to provide a means to improve upon the weaknesses of traditional photoinitiated polymerizations. The free radical polymerization of thiol and –ene monomers occurs via a series of free radical chain transfer events, as a result, …

Comparison Of Liquid-Liquid Extraction And Solid Phase Extraction Of Mephedrone, Brittany Simone Love

Master's Theses

Legal high drugs are modified scheduled drugs. As with any new drug, researchers have to conduct studies to gather information about the drug. The problem with obtaining accurate information on new drugs is that by the time information is gathered, drug abusers and street chemists have developed new ones. Comparing designer drugs to their illegal counterparts is often helpful in that it can provide a starting point. Mephedrone is a new designer drug that has become a problem over the past few years. Often marketed as bath salts and plant food, mephedrone has become the knockoff replacement for amphetamines. This …

Growth And Carboxysome Composition Of The Csosia Pore Mutants Of Halothiobacillus Neapolitanus, Jenifer Milam

Master's Theses

Carboxysomes are specialized organelles that are filled with ribulose 1,5- bisphosphate carboxylase/oxygenase (RubisCO) needed for CO2 fixation. The major carboxysome shell proteins, CsoSl A, B, and C, form hexamers which tile together to form the facets of the thin shell. Each hexamer has a small central pore that may play a role in metabolite flux. Using predicted structural models, a specific amino acid within the conserved hexamer pore motif (Phe-Val-Gly-Gly-Gly-Tyr) was chosen to change the size and charge of the pore, respectively. Two mutants of Halothiobacillus neapolitanus were generated in which the wild type csoSJA gene was replaced with the …

On The Currents And Transports Connected With The Atlantic Meridional Overturning Circulation In The Subpolar North Atlantic, X. Xu, H. E. Hurlburt, W. J. Schmitz Jr., R. Zantopp, J. Fischer, P.J. Hogan

Faculty Publications

Results from an interannually forced, 0.08 degrees eddy-resolving simulation based on the Hybrid Coordinate Ocean Model, in conjunction with a small but well-determined transport database, are used to investigate the currents and transports associated with the Atlantic meridional overturning circulation (AMOC) in the subpolar North Atlantic (SPNA). The model results yield a consistent warming in the western SPNA since the early 1990s, along with mean transports similar to those observed for the trans-basin AMOC across the World Ocean Circulation Experiment hydrographic section AR19 (16.4 Sv) and boundary currents at the exit of the Labrador Sea near 53 degrees N (39.0 …

Polymer Surface Engineering Via Thiol-Mediated Reactions, Ryan Matthew Hensarling

Dissertations

Synthesis of polymer brushes to decorate a surface with desired functionality typically involves surface-initiated polymerization (SIP) of functional, but non-reactive monomers. This approach suffers major drawbacks associated with synthesizing sufficiently thick polymer brushes containing surface-attached polymer chains of high molecular weight at high grafting density (i.e. cost, synthetic effort and functional group intolerance during polymerization). The research herein seeks to circumvent these limitations by the decoration of surfaces with polymer chains bearing specific pendent functional groups amenable to post-polymerization modification (PPM). In particular, this dissertation leverages PPM via a specific class of click reactions – thiol-click – that 1) enables …

Understanding Corrosion Protection And Failure Through Model Polymers In Thin Films, Joshua Smith Hanna

Dissertations

When developing a model polymeric system to facilitate in the detection of molecular and microscopic events that preface macroscopic corrosive failure; a better understanding of how polymers can indicate corrosion was accomplished. Initially, the thought that molecular chain scission as a necessity for corrosion to occur had to be tested. Through the utilization of high molecular weight thermoplastic (HMWTP) model polymers, it was found that corrosion protection did not correlate to the quantity of weak bonds within an epoxy-amine polymer matrix. Therefore more sensitive methods of detecting corrosion had to be developed since changes within the polymer matrix did not …

Magnesium-Based Sacrificial Anode Cathodic Protection Coatings (Mg-Rich Primers) For Aluminum Alloys, Shashi S. Pathak, Sharathmukar K. Mendon, Michael D. Blanton, James W. Rawlins

Faculty Publications

Magnesium is electrochemically the most active metal employed in common structural alloys of iron and aluminum. Mg is widely used as a sacrificial anode to provide cathodic protection of underground and undersea metallic structures, ships, submarines, bridges, decks, aircraft and ground transportation systems. Following the same principle of utilizing Mg characteristics in engineering advantages in a decade-long successful R&D effort, Mg powder is now employed in organic coatings (termed as Mg-rich primers) as a sacrificial anode pigment to protect aerospace grade aluminum alloys against corrosion. Mg-rich primers have performed very well on aluminum alloys when compared against the current chromate …

The Effect Of Poss Modified Montmorillonite On Elastomer Nanocomposites, Elana Celeste Lewis

Master's Theses

The goal of this thesis was to define the structural factors that determine performance in clay/rubber nanocomposites when polyhedral oligomeric silsesquioxane (POSS) is used as a dispersant. POSS has been shown previously to enhance clay, metal oxides, and carbon nanotube dispersion in thermoplastics matrices, but their performance in rubber systems has not yet been explored. There is little fundamental understanding of how POSS interacts with clay and how these modified fillers react with rubber matrices. This thesis aims to develop a greater understanding of the mechanisms of POSS-clay modification through the examination of two different POSS-clay systems and their effect …

Producing Data To Support The Detection And Understanding Of Early On-Set Corrosion In Accelerated Weathering, Stephanie Suzanne Messer

Master's Theses

The goal of the research reported herein was to generate data towards the development of methods and protocols for detecting, quantifying, and understanding early on-set corrosion events on and above aluminum 2024-T3. The studies focused on incorporating two main fluorescent probes into a few model epoxy and/or urethane coatings to detect X and Y axis specific pH changes occurring upon and above the substrate during pre-macroscopic corrosion. The primary fluorophore used was fluorescein, a pH sensitive probe capable of detecting the changes, mainly increases in pH that accompanies aluminum corrosion. The second molecular probe, rhodamine B, was utilized to better …