Chemistry Commons^™

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 …

Metal-Organic And Supramolecular Architectures Based On Mechanically Interlocked Molecules, Isurika Rosini Fernando

Dissertations

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials.

Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, …

Synthesis And Characterization Of New Light Emitting Probes For Sensitive Detection Of Bio-Molecules And Live Cells, Shyamala Pravin Pillai

Dissertations

A variety of contemporary analytical platforms in technical and biological applications take advantage of labeling the objects of interest with fluorescent or luminescent tracers. Luminescent tracers take advantage of the unique property of some lanthanide metals to absorb and emit light. Long lifetime of lanthanide emission allows temporal gating of the signal, which avoids the short-lived background of interfering sample components. This property in combination with large Stokes shift contributes to extreme sensitivity of detection (ca. 10^-13-10^-14 M), which makes lanthanide-based probes suitable for large variety of challenging tasks ( e.g., intracellular detection of single DNA/RNA, or …

Development Of Luminescent Probes For Ultrasensitive Detection Of Biopolymers, Their Complexes, And Living Cells, Laura A. Wirpsza

Dissertations

New luminescent probes with enhanced brightness convenient for bioconjugation were synthesized and tested in major biological applications including the detection of nucleic acids and living cells. The first project used luminescent lanthanide ion probes that take advantage of hyper-sensitive acquisition of their long-lived emission signal in time- resolved mode, which avoids short-lived background fluorescence of the medium. Two model carbostyril fluorophores (cs 124-CH₃ and cs 124-CF₃) were modified by inclusion of two spacers (diamino and bi-phenyl) for the attachment of amine and thiol reactive cross-linking groups. In this project, time-resolved measurements are presented for spectroscopy and microscopy. …

The Rich Chemistry Of Cyclotriveratrylene (Ctv) And Ct-Inspired Reactions: Anthracenes With Organic Light-Emitting Diode (Oled) Applications And The Discovery Of Cascade Reactions, Samuel Sarsah

Dissertations

Cyclotriveratrylene (CTV) is a supramolecular scaffold with applications in host-guest chemistry, analytical detection, drug delivery and liquid crystals. We have discovered that CTV rearranges to a highly functionalized anthracene derivative that is ideal for the synthesis of 9,10-disubstituted anthracene derivatives that are useful for the construction of organic light-emitting diodes (OLEDs). Several diaryl anthracene derivatives have been synthesized and analyzed, and were found to have excellent electroluminescent properties, including one analog that exhibits an exceptionally high quantum yield. Red, green and blue are the primary colors needed for full color display, but blue fluorescence emitting organic compounds used in OLEDs …

Use Of Sweet Potato To Develop A Medium For Cultivation Of Lactic Acid Bacteria, Saeed A. Hayek

Dissertations

This study investigated the use of sweet potatoes (Ipomoea batatas) as a basic component to develop a medium for cultivation of lactic acid bacteria (LAB). Extract from baked sweet potatoes was used to form a sweet potato medium (SPM). SPM was supplemented with 4 g/L of each nitrogen source (beef extract, yeast extract, and proteose peptone #3). Lactobacilli MRS was used as a control medium. Ten LAB strains were used to determine the suitability of SPM serving the growth of LAB. Our results showed no significant (p < 0.05) differences in the optical density, maximum specific growth rates, and bacterial populations between MRS and SPM. SPM also maintained higher pH values throughout the incubation period compared to that in MRS. The cost of SPM was 47% less than the cost of MRS. Further step was taken to determine the suitability of SPM serving LAB enzymatic activity. LAB strains growing in SPM showed relatively higher β-glucosidases, acid phosphatase, and phytase activities and lower a-glucosidase compared to that in MRS. Strains of L. reuteri showed the …

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 …

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 …

Nanoporous Gold As A Solid Support For Protein Immobilization For The Development Of Immunoassays, And For Biomolecular Interaction Studies, Binod Prasad Pandey

Dissertations

Nanoporous gold (NPG) is a versatile material of high surface area to volume ratio that can be readily modified with self-assembled monolayers of alkanethiols to which biomolecules can be linked. NPG presents new opportunities for the development of immunoassays, and for the development of carbohydrate based assays. This thesis explores the use of NPG as a support for self-assembled monolayers, their linkage to antibody-enzyme conjugates for immunoassay development, and for the study and application of carbohydrate-protein interactions. Direct kinetic electrochemical immunoassays were developed on NPG for prostate specific antigen (PSA) and carcinoembryonic antigen (CEA). The decrease in enzymatic conversion of …

Synthesis And Catalytic Applications Of Platinum(Ii) And Palladium(Ii)-Pta And Dapta Complexes, Sitaram Acharya

Dissertations

The cage-like tertiary phosphine, 1,3,5-triaza-7-phosphaadamantane (PTA) has recently received interest because of its water-solubility, air-stability, non-ionic, non-surfactant, and basic nature. These properties can solubilize transition metal complexes in the aqueous phase. A related air-stable derivative, N,N’-diacetyl-1-3-5-triaza-7-phosphaadamantane (DAPTA) has greater water-solubility than PTA, however, its coordination chemistry has not been significantly explored. This study involved the synthesis and characterization of a series of novel air-stable and water-soluble four-coordinated dialkyl, dialkynyl, dihalo, and halo(alkyl) complexes of platinum and palladium bearing PTA and DAPTA ligands. The alkyl complexes of the type MX(R)P2 (M = Pt, Pd; X = Cl, Br, I; R = …

Nickel Catalyzed Homoallylation Reactions And Synthesis Of Potent Inhibitors Of Yoph, Mahesh Prasad Paudyal

Dissertations

Amphidinolides are cytotoxic natural products isolated from marine dinoflagellate Amphidinium species. Amphidinolides C, C2 and F are active against cancer cell lines. Homoallylation of aldehydes with isoprene and triethylborane catalyzed by Ni(acac)2 gave hydroxyalkenes in good yield with excellent regio- and stereoselectivity. Cross metathesis of the hydroxyalkenes with methyl acrylate using second-generation Grubbs catalyst and copper(I) iodide afforded α,β-unsaturated esters, which underwent cyclization in the presence of DBU to produce tetrahydrofurans with the correct relative configuration for the C1-C9 fragment of amphidinolides C, C2, and F. Homoallylation of chiral and achiral diene carboxylate esters and dienecarboxamides with various aldehydes were …

Studies Toward Tetrahydrofuran-Containing Natural Products: Total Synthesis Of Amphidinolide C And Oxylipids, Sudeshna Roy

Dissertations

Tetrahydrofurans (thf) and tetrahydropyrans (thp) are important structural motifs found in a broad array of biologically relevant natural products such as polyether antibiotics and acetogenins. Classic methods used for thf- or thp-ring synthesis have their own advantages and disadvantages which tend to be substrate specific. Therefore, development of new and efficient methods is imperative especially to address the issue of diastereoselectivity when attainment of both cis- and trans-2,5-thf (or 2,6-thp) is highly desirable. Herein, a strategy of cross-metathesis and Pd(0)-catalyzed cyclization, useful for obtaining both cis- and trans-2,5-disubstituted thf (or 2,6-disubstituted thp), will be discussed along with its application in …

Investigating The Biochemical Activity Of Some Flavonoids, Coumarins And Modified Gold-Nanoparticles As Anti-Breast-Cancer Agents, Amr Ezzat Mohamed Mahmoud

Dissertations

Polyphenols compounds are abundant natural products found in many plants as secondary metabolites. These compounds display many interesting pharmacological activities, which have motivated chemists over the years to explore them, and their synthetic derivatives, as potential drugs, especially anticancer drugs. Breast cancer is the most common cancer in women globally, and in the United States of America the estimated worldwide new breast cancer cases and the number of deaths are 1.38 million and 458 thousand, respectively. Currently in the USA there are 2.6 million women who have been treated for breast cancer, and the estimated number of deaths are 39,520 …

New Dual Initiators For Polyisobutylene-Based Block And Star Polymers, Yaling Zhu

Dissertations

Polyisobutylene (PIB), available solely by living carbocationic polymerization (LCP), is a commercially important polymer with excellent thermal stability, good flexibility and extraordinary impermeability to gases. Due to these attractive properties, coupling PIB to other polymer blocks is expected to result in new and useful products. Two types of new dual initiators possessing initiating sites for both LCP and atom transfer radical polymerization (ATRP), have been designed for the preparation of AB linear and A2B miktoarm star copolymers, where A is PIB-based block copolymer that grows cationically and B is polyacrylate or other radically-derived polymer block, without intermediate modification.

Mono-cationic mono-radical …

Modern Approaches For Multifunctional Hydrolyzying Thiol-Ene Networks, Nicole Marie Mackey

Dissertations

Marine fouling has been an expensive and time-consuming process for navies and fishermen by the accumulation of marine algae and animals on artificial surfaces. Many coatings have been proposed to combat marine fouling in efforts to extend the lifetime of objects immersed in sea water. However, all coatings tested have either failed to resist fouling for a significant length of time or have released toxins into the environment. We have investigated an environmentally friendly approach to address the problem of marine fouling through the synthesis and preparation of a biocidal and a self-polishing coating. Both novel monomers were prepared containing …

Molecular Network Development Of A Thermosetting Epoxy-Amine Polymer, Christopher Michael Sahagun

Dissertations

i ABSTRACT MOLECULAR NETWORK DEVELOPMENT OF A THERMOSETTING EPOXY-AMINE POLYMER by Christopher Michael Sahagun May 2012 Epoxy-amine resins find wide application as the matrix material of high performance polymer composites due to their favorable mechanical properties, thermal properties and solvent stability. These properties are derived from the complicated, highly crosslinked molecular network that is characteristic of these thermoset polymers. The connectivity of the molecular network has a strong influence on the physical performance of the finished part. Non-homogeneity in the network structure can degrade these favorable properties through the introduction of low-energy pathways for solvent penetration or fracture propagation. This …

Surface, Bulk, And Rheological Properties Of Polyhedral Oligomeric Silsesquioxane/High Density Polyethylene Nanocomposites, Robert Douglas Cook Jr.

Dissertations

In the formulation of high performance nanocomposites, control of miscibility and dispersion of filler material through a polymer matrix is of utmost importance. Due to their inorganic nature most nanofillers are insoluble in polymers, leading to costly/complicated surface modification as a primary means of increasing miscibility and interaction with organic matrices. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals offer an attractive alternative to conventional nanofillers. Due to their hybrid organic-inorganic nature, POSS has the potential to be tailored for miscibility in a wide range of organic matrices not by chemical surface modification but through modification of the molecular structure of the …

A Bisphenol-A-Based Resin System That Cures Via Triazole Ring Formation For Marine Composite Applications, Irene Elizabeth Gorman

Dissertations

Large composite panels, such as those utilized in marine applications, cannot be economically cured in an autoclave. For these structures the elevated temperatures necessary to achieve high crosslink density must come from the curing reaction itself. We are developing a resin system that cures via triazole ring formation (cycloaddition reaction of azides with terminal alkynes) instead of the traditional oxirane/amine reaction. The high exothermicity of the azido/alkyne reaction is expected to yield higher extents of reaction under ambient-cure conditions, making the resin system potentially suitable for "out-of-autoclave" curing processes. This work was conducted through a multi-tiered approach involving synthesis, kinetic …

Optical And Electrochemical Properties Of Monolayer Protected Gold Clusters Modified With Fluorophores, Mary Sajini Devadas

Dissertations

My research focused on the synthesis, characterization and the investigation of the optical and electrochemical properties of monolayer-protected quantum-sized gold clusters. Significant research attention was focused on the solution phase optical and electrochemical properties of these clusters. Highly monodisperse Au clusters with different types of ligands were successfully synthesized with sizes varying from 1 nm to 13 nm. These preformed gold clusters were modified with fluorophores and pseudo-rotaxanes for developing better nonlinear optical materials for sensing and biological imaging purposes. We have tried to focus on the interaction of the outer ligand shell, made up of –S-Au-S-Au-S- bonds, with the …

Optical And Electrochemical Sensors For The Detection Of Metal Ions And Nerve Gas Mimics Via Fluorescein And Coumarin Derivatives, Fasil Adefris Abebe

Dissertations

Trace element detection of metals, for example, iron, Copper and zinc, are important in biological systems and in the environment. Many of us are aware that our cells contain metal ions that are “tied” up in proteins. However, chelatable or “free” trace elements can also be found in small quantities, and can have a negative impact on our bodies. Despite the increasing surge in developing sensors for metals and nerve gas agents, efficient detection still remains a challenge. Among the various sensors developed so far, fluorescence sensors play an important role due to their simplicity. I design fluorescein-based chemosensors for …

Superarmed Glycosyl Donors In Chemical Glycosylation, Hemali Deepthika Premathilake

Dissertations

Only recently has the tremendous biological significance and therapeutic potential of carbohydrates and conjugates thereof (glycoproteins, glycolipids, proteoglycans, etc.) begun to emerge. As the appreciation for the biological roles of carbohydrates a growing demand for efficient and scalable methods towards the synthesis of these challenging molecules has become even more imperative. This has led to the development of a variety of expeditious strategies for oligosaccharide assembly. Amongst these strategies, the so-called armed-disarmed strategy introduced by Fraser-Reid is of particular attractiveness as it allows for chemoselective oligosaccharide synthesis. Recently, the conformational changes as well as the strategic placement of common protecting …

Analysis Of Illicit Drugs, Their Metabolites And Other Micropollutants In Water By Liquid Chromatography Tandem Mass Spectrometry, Deepika P. Panawennage

Dissertations

The goal of this project is to develop liquid chromatography tandem mass spectrometry (LC/MS/MS) methods for the analysis of different, novel micropollutants in waste water and natural water. Micropollutants are compounds that can exert adverse environmental and human health effects at low concentrations. Most of these compounds include personal care products and pharmaceuticals, such as antibiotics and controlled substances. In the first part of this study, we focused in the analysis of illicit drugs and drug metabolites because these analyses have the potential to serve as markers of drug abuse. We have detected over sixteen different illicit drugs and their …

Spectroelectrochemical Studies Of The Reductive Intermediates Of Anthraquinone-2,6-Disulfonate In Aqueous Media, Anna Weiss

Dissertations

Reactive intermediates in the reduction of anthraquinone-2,6-disulfonate (AQDS) by dithionite combine to form a transient dimer which has shown to give rise to a series of charge transfer bands in the visible range (600-750 nm). Additional wavelengths associated with these intermediate species have been observed at wavelengths 402, 444 and 510 nm. These transient intermediates are generated as dithionite decomposition products re-oxidize AQDS. Evidence of the dimer was also found in experiments in which reduction of AQDS was achieved electrochemically by the use of a potentiostat. This implies three things: 1. dithionite is not required for dimerization of reactive intermediates; …

Study Of The Vaporization Enthalpies By Correlation-Gas Chromatography, Dmitry Lipkind

Dissertations

The focus of this thesis is on the measurement and collection of thermodynamic and physical property data, including vaporization, fusion, and sublimation enthalpies and vapor pressures of large n-alkanes, nitrogen heterocycles and related compounds by a technique developed in our laboratory referred to as correlation-gas chromatography (C-GC). These thermodynamic data are of importance to several disciplines that include chemical engineering, as well as the pharmaceutical and the petrochemical industries. Vapor pressures of large hydrocarbons are fundamental data required in the petroleum industry to develop thermodynamic models for dealing with crude oil. Environmental chemists and engineers use vapor pressures and vaporization …

Synthesis And Characterization Of Acceptor: Donor Block Copolymers For Organic Photovoltaics, Brandon Cory Achord

Dissertations

Mankind needs sources of clean power. Photovoltaic (PV) cells, in use since 1839, have proven reliable and practical for certain applications. PV cell efficiency has changed over the years from 1-2% to ultra-high efficiency cells operating at efficiencies greater than 40%. Organic photovoltaics are a potential transformative technology platform. The potential for cell use, efficiency and cost are all parts of the research and development focus at the time this document was written. This research was initiated with a focus on the synthesis and understanding of the variables effecting acceptor-donor block copolymer. The self-assembled morphology resulting from varying volume ratios …

Physical And Electrical Properties Of Trimetallic Nitride Template Endohedral Metallofullerenes And Their Polymer Nanocomposites, Hanaa Mohammed Ahmed

Dissertations

The main objective of this study was characterization of pure metallic nitride fullerene, MNF, and MNF containing polymers to evaluate these materials as suitable devices for tunable applications. Polymer-fullerene nanocomposites consisting of linear polyurethane (PU) segments crosslinked via polyhydroxylated fullerenes (C₆₀ and Sc₃N@C₈₀, a metallic nitride fullerene) were prepared and characterized for their mechanical and dielectric properties using dynamic mechanical analysis (DMA) and broadband dielectric spectroscopic techniques. Polyhydroxylated fullerenes C₆₀(OH)₂₉ and Sc₃N@C₈₀(OH)₁₈ were synthesized in a high yield through a solid-state high sheer ball-milling procedure and were …

The Investigation Of Asphaltene-Naphithenic Acid And Asphaltene-Surface Interactions, David Tristan Heaps

Dissertations

Asphaltenes represent a ubiquitous problem in the oil industry due to their adverse effects on recovery, production, and processing equipment. These problems have affected oil companies throughout the world, resulting in significant financial losses. In order to expand the existing body of knowledge related to asphaltenes, we have examined how the presence of naphthenic acids contributes to the particle aggregation and sedimentation behavior of asphaltene suspensions as well as how the physics and chemistry of a substrate affect asphaltene adsorption/deposition.

The flocculation of asphaltenes in the presence of naphthenic acids was investigated using dynamic light scattering (DLS), near-infrared spectroscopy (NIR), …

Development And Utilization Of Digital Image Correlation Techniques For The Study Of Structural Isomerism Effects On Strain Development In Epoxy Network Glasses, Stephen Robert Heinz

Dissertations

The specific aim of this dissertation is to present the findings regarding the effects of molecular structure on macroscopic mechanical performance and strain development in epoxy networks. Network molecular structure was altered through monomer isomerism and crosslink density/molecular weight between crosslinks. The use of structural isomerism provided a pathway for altering mechanical performance while maintaining identical chemical composition within the network. Isomerism was investigated primarily by the curing of diglycidyl ether of bisphenol A (DGEBA) using either the para- or meta-substituted derivatives of diaminodiphenyl sulfone (DDS). Additional insights into isomerism were gained through the investigation of networks composed of either …

Effects Of Molecular Architecture On Fluid Ingress Behavior Of Glassy Polymer Networks, Matthew Blaine Jackson

Dissertations

This manuscript demonstrates the synthesis of glassy polymer network isomers to control morphological variations and study solvent ingress behavior independent of chemical affinity. Well-controlled network architectures with varying free volume average hole-sizes have been shown to substantially influence solvent ingress within glassy polymer networks. Bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), Triglycidyl p-aminophenol (pAP, MY0510), Triglycidyl maminophenol (mAP, MY0610), and tetraglydicyl-4,4’-diamino-diphenyl methane (TGDDM, MY721) were cured with 3,3’- and 4,4’-diaminodiphenyl sulfone (DDS) at a stoichiometric ratio of 1:1 oxirane to amine active hydrogen to generate a series of network architectures with an average free volume hole-size (V_h) …