Chemistry Commons^™

Photopolymerized Thiol-Ene Networks For Gas Barrier And Membrane Applications, Luke Kwisnek

Dissertations

Gas transport and free volume properties of photopolymerized thiol-ene networks for various applications are reported. For basic, commercially-available thiol-ene formulations, oxygen permeation was strictly dependent on the difference between T_test (room temperature for this work) and network T_g. Networks with T_g near T_test demonstrated the lowest values of permeability, diffusivity, and solubility. A robust, high-barrier network was selected for further modification. New networks with embedded functionality were formed using a two-step approach. Thio-Michael addition of a tetrathiol to monofunctional acrylates formed new functional thiol monomers. These functional thiols were combined with an isocyanurate-based triene and …

Resorbable Polymer-Hydroxyapatite Composites For Bone Trauma Treatment: Synthesis And Properties, Troy E. Wiegand

Department of Chemistry: Dissertations, Theses, and Student Research

Contemporary therapies for hard tissue replacement involve allographs, where the donor and recipient are of the same species, or the use of xenogenic transplants.  Intraspecies materials are often in short supply and interspecies materials are subject to immunological barriers such as disease and tissue rejection.  Synthetic composites are unencumbered by these limitations.  Poly lactic acid (PLLA) and its copolymers have been used in medicine due to their ability to be resorbed by the body without adverse effects.  PLLA’s are currently most commonly used in resorbable sutures and gauzes, but there is increasing interest in using them in conjunction with hydroxyapatite …

Sequencing Of Amine Nucleoside Polymers: Understanding The Fidelity Of Dna-Directed Reductive Amination, Sarah M. Anderson

Honors Student Works

DNA replication is a form of template-directed polymerization that occurs with the aid of numerous enzymes. By developing a DNA replication mimic that can undergo template-directed polymerization without enzymes, the scope of template-directed polymerization will be broadened beyond biological systems. One template-directed polymerization method that has proven successful is reductive amination on a DNA template, a two-step polymerization reaction involving equilibrium imine formation followed by reduction of the imine to the amine. Because DNA-directed reductive amination is an information transfer system, it should proceed with fidelity; however, the extent of fidelity must be explored. These studies will require the ability …

Evaluation Of Stain Blocking Primer Coatings With Low Volatile Organic Compound (Voc) Content And Effects Of Drying Conditions On The Properties Of Water Reducible Coatings For Polypropylene, Megan Alexandra Hart

Master's Theses

The California Air Resources Board (CARB) plans to reduce the volatile organic compound (VOC) limit of specialty primers, sealers, and undercoaters (SPSU), also referred to as stain blocking primers, from 350 g/L to 100 g/L in January of 2012. These coatings are primarily used as stain blocking primers over a variety of substrates, such as wood and drywall. Currently the stain blocking primers that are considered most effective are solvent based primers that contain VOC levels much higher than 100 g/L. The goal of this study is to determine if primers on the market today with a VOC content of …

Micro- And Nanoparticles In Uv-Cured Thin Films, T. Christopher Corkery, Joseph Chan, Mike J. Idacavage, Elizabeth R. Gillies, Paul J. Ragogna

Chemistry Presentations

No abstract provided.

Ionic Conductivity And Related Studies In Methyl Cellulose Based Polymer Electrolytes And Application In Supercapacitors., Noor Erwani Azura Shuhaimi

Student Works (2010-2019)

Solid polymer electrolytes based on methyl cellulose (MC) were investigated. Two MC based polymer electrolytes systems were prepared using solution cast technique. These are MC-ammonium nitrate (NH4NO3) system and MC-NH4NO3 system plasticized with poly (ethylene glycol), (PEG). NH4NO3 was chosen as the proton source to make MC, a biodegradable polymer conductive. The room temperature conductivity of pure MC is 3.08 × 10-11 S cm-1. The conductivity is increased up to 2.10 × 10-6 S cm-1 with addition of 25 wt.% NH4NO3. To enhance conductivity of MC-NH4NO3 system, PEG was added to 75MC25AN solution in different concentrations (from 5 to 25 …

Copolymerization Of Methyl Methacrylate With Palm Oleic Acid-Based Macromers And Application Of The Copolymers As Coating Materials., Shahla Ataei Kachouei

Student Works (2010-2019)

This study concerns the synthesis and characterization of three different palm oleic acid-based macromers made from oleic acid, together with phthalic anhydride and glycerol. The molecular structure of the macromers had been varied by using 28, 40 and 65 wt% of oleic acid in the overall formulation and labeled as AlkOA28, AlkOA40 and AlkOA65 respectively. The extent of reaction at the end of polycondensation reaction in making each macromer was more than 95%. Thermal degradation studies of three macromers revealed that AlkOA28 macromer has a relatively higher thermal stability and followed by AlkOA40 and AlkOA65. From Kissinger method, activation energy …

Encapsulation And Release Of Small Molecules From Polymeric Micelles, Monica Boatwright

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Synthesis And Characterization Of Self-Healing Poly (Carbonate Urethane) Carbon-Nanotube Composites, Roger Wesley Bass

USF Tampa Graduate Theses and Dissertations

Synthesis of high molar mass polycarbonate polyurethanes using a novel polyol is described. The resulting elastomers demonstrate excellent mechanical properties as well as the capability to re-heal after rupture without the addition of additives or imbedded healing agents. The self-healing functionality is shown to greatly improve with the addition of up to 1% single and multi-walled carbon nanotubes. The interface of the carbon nanotubes and self-healing polymer are probed using Raman techniques and provide an insight into how the self-healing actions are improved with the addition of carbon nanotubes.

Synthesis of polycarbonate polyurethanes and carbon nanotube composites using a novel …

Bulk Modulus Of Poly(N-Isopropylacrylamide) Microgels Through The Swelling Transition, B. Sierra-Martin, Y. Laporte, A. B. South, L. Andrew Lyon, A. Fernandez-Nieves

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report measurements of the bulk modulus of individual poly(N-isopropylacrylamide) microgels along their swelling transition. The modulus is determined by measuring the volume deformation of the microgel as a function of osmotic pressure using dextran solutions. We find that the modulus softens through the transition, displaying a nonmonotonous behavior with temperature. This feature is correctly reproduced by the theory of Flory for polymer gels, once the concentration dependence of the solvency parameter is properly incorporated.

Synthesis And Physicochemical Properties Of Cationic Microgels Based On Poly(N-Isopropylmethacrylamide), Xiaobo Hu, Zhen Tong, L. Andrew Lyon

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Surfactant-free, radical precipitation copolymerization of N-isopropylmethacrylamide and the cationic co-monomer N-(3-aminopropyl) methacrylamide hydrochloride (APMH) was carried out to prepare microgels functionalized with primary amines. The morphology and hydrodynamic diameter of the microgels were characterized by atomic force microscopy and photon correlation spectroscopy, with the effect of NaCl concentration and initiator type on the microgel size and yield being investigated. When a 2,2'-azobis (2-amidinopropane) dihydrochloride (V50)-initiated reaction was carried out in pure water, relatively small microgels (similar to 160 nm in diameter) were obtained in low yield (similar to 20%). However, both the yield and size increased if the reaction was …

Hybrid Micro-/Nanogels For Optical Sensing And Intracellular Imaging, Weitai Wu, Shuiqin Zhou

Publications and Research

Hybrid micro-/nanogels are playing an increasing important part in a diverse range of applications, due to their tunable dimensions, large surface area, stable interior network structure, and a very short response time. We review recent advances and challenges in the developments of hybrid micro-/nanogels toward applications for optical sensing of pH, temperature, glucose, ions, and other species as well as for intracellular imaging. Due to their unique advantages, hybrid micro-/nanogels as optical probes are attracting substantial interests for continuous monitoring of chemical parameters in complex samples such as blood and bioreactor fluids, in chemical research and industry, and in food …

Two-Phase Partitioning System Using Elvax 40w Polymer For The Biodegradation Of Aqueous Phenols, Amit Suresh Ghode

Masters Theses & Specialist Projects

A solid-liquid two phase partitioning system (TPPS) is a new technology platform for destroying toxic organic compounds. TPPS have traditionally been operated by using an immiscible organic phase which partitions organic compounds into the aqueous phase. TPPS using an immiscible organic phase suffers from several limitations such as the organic phase could be biodegradable and hence only certain compatible microbial strains could be used. This therefore, eliminates the desired use of mixed microbial populations for efficient degradation. A solid-liquid two phase partitioning system, in which solid polymeric beads replace liquid organic phase, appears to have benefits over the traditional liquid-liquid …

The Influence Of Nanoporous Crystalline Structure On Low Molecular Weight Mass Transport In Syndiotactic Polystyrene, Justin Paul Brandt

Dissertations

Solid-state structure, crystalline morphology, crystallization kinetics, thermal, free volume, and gas transport properties of semicrystalline syndiotactic polystyrene (sPS) and ethylene vinyl alcohol copolymers (EVOH) have been investigated. Solid-state structure of sPS after crystallization from the melt and glassy state was examined by differential scanning calorimetry (DSC), density and wide angle x-ray diffraction analysis (WAXD). The measurements confirmed low density of syndiotactic polystyrene crystalline forms, which in the case of α and δe was smaller and in the case of β and γ crystalline forms was slightly larger than the density of the glassy amorphous sPS. Positron annihilation lifetime spectroscopy (PALS) …

Study Of 3,3' Vs. 4,4' Dds Isomer Curatives On Physical Properties And Phenyl Ring Motions Of Dgeba Epoxy Via Molecular Dynamics, Deuterium Nmr, And Dielectric Spectroscopy, Samuel James Tucker

Dissertations

The purpose of this research is to develop a multiscale understanding of crosslinked amorphous matrices, connecting molecular level events to macroscopic properties. To accomplish this goal, our methodology was to identify network architectures that influence molecular level energy dissipation through mechanisms such as bond rotations, torsions, and ring flips and then relate those molecular motions to macroscopic properties. Studies were accomplished on two aerospace grade matrices: the epoxy, diglycidyl ether of bisphenol A (DGEBA) cured with two amines, 3,3’- diaminodiphenyl sulfone (33DDS) and 4,4’-diaminodiphenyl sulfone (44DDS). The 33DDS/DGEBA and 44DDS/DGEBA served both to provide a baseline for experimental testing of …

Synthesis And Electrical Properties Of Functional Block Copolymer/Inorganic Nanocomposite Materials, Hongying Chen

Dissertations

Sulfonated poly[styrene-b-ethylene-co-butylene-b-styrene] (sSEBS) block copolymers/inorganic nanocomposite materials were synthesized via in situ formation of inorganic fillers and characterized particularly for their dielectric properties and proton conductivities.

In preparation of sSEBS/SrTiO₃ nanocomposites, titanium (IV) isopropoxide [Ti(OPrⁱ)₄] complex was diffused into sSEBS film, followed by subsequent hydrolysis of [Ti(OPr i)4], diffusion of strontium cations in sSEBS domains, and in situ formation of crystalline SrTiO₃. sSEBS with sulfonation degree of 38.1% and 65.0% were employed, and relevant sSEBS/SrTiO₃ composites contain SrTiO₃ of 10-15 wt%. Elemental composition characterization with ESEM/EDX indicated uniform distribution of …

Unusually Conductive Carbon-Inherently Conducting Polymer (Icp) Composites: Synthesis And Characterization, Shawn Edward Bourdo

Theses and Dissertations

Two groups of materials that have recently come to the forefront of research initiatives are carbon allotropes, especially nanotubes, and conducting polymers-more specifically inherently conducting polymers. The terms conducting polymers and inherently conducting polymers sometimes are used interchangeably without fully acknowledging a major difference in these terms. Conducting polymers (CPs) and inherently conducting polymers (ICPs) are both polymeric materials that conduct electricity, but the difference lies in how each of these materials conducts electricity. For CPs of the past, an electrically conductive filler such as metal particles, carbon black, or graphite would be blended into a polymer (insulator) allowing for …

On-Metal Synthesis Of Some Aryl Substituted Rhenium Η5 Cyclopenta[C] Pyridazyl Complexes, Phenahas Gandu Sriramulu

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole) and their derivatives have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). We are interested in synthesizing organometallic pyridazines and rhenium pyridazyl complexes for polymer research. SeveraI5,6-fused ring pyridazines (1,2-CsH3(CRNH)(CRN) have been synthesized and characterized. Additionally, pyridazyl complexes of rhenium were synthesized in three steps beginning from fulvenes 1,2-CsH3(COHR)(COR). On-Metal synthesis and characterization of (Re(CO)3 {1,2- CSH3(CRN)(CRN)}] (R=C6RtOMe, C6RtCI, C4H30) and some off-metal pyridazines are reported here. Our research is focused on synthesis of a variety of 5,6- fused …

Synthesis And Characterization Of Photoactive Amorphous Molecular And Polymeric Pyridinium Materials, Alexi Kamenov Nedeltchev

UNLV Theses, Dissertations, Professional Papers, and Capstones

Pyridinium materials both molecular and polymeric are interesting class of multifunctional electrolytes and polyelectrolytes, which exhibit liquid-crystalline and light-emitting properties. Moreover, their properties could be easily tuned simply by modifying the chemical structures of counterions.

In this dissertation, we described the preparation and analysis of new ionic molecular materials based on bis(pyridinium salt)s and a new class of poly(pyridinium salt)s with various heterocyclic moieties in their backbones with various organic counterions. They were prepared by either ring-transmutation reaction or by metathesis reaction. Their chemical structures were confirmed by FTIR, 1H and 13C NMR spectroscopy and elemental analysis. They had excellent …

Structure-Property Correlation In Cyclopolymerization Of New Acrylate-Based Functional Monomers, Huseyin Tas

Dissertations

New ether dimer; (ED-Od) and (ED-Eh) and diester; (ODE) and (EHDE) derivatives of α-(hydroxymethyl)acrylate, each having two octadecyl and 2-ethylhexyl side chains respectively, and an amine-linked di(2-ethylhexyl)acrylate (AL-Eh), having three 2-ethylhexyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature, Tg. The free radical polymerizations of these monomers yielded high molecular weight polymers. Cyclopolymer formation of ED-Od, ED-Eh and AL-Eh was confirmed by 13C NMR analysis and the cyclization efficiencies were found to be very high (~100%). Copolymers of ED-Od, ODE, ED-Eh, EHDE, …

Design, Synthesis, And Polymerization Of Novel Heterocyclic Monomers As Precursors For Functional Polyester, Poly(Ester Amide)S And Polyamides, Eylem Tarkin-Tas

Dissertations

The research presented in this dissertation involves the synthesis and polymerization of heterocyclic monomers which pave the way to biodegradable polyester nanocomposites, functional polyesters or poly(ester amide)s, functional polyamides and supramolecular polymers. The key monomers are ε-caprolactone, γ-acetamido-ε- caprolactone, γ-ethylene ketal-ε-caprolactam and α-amino-ε-caprolactam.

Poly(ε-caprolactone) organo-modified montmorillonite nanocomposites were prepared by in-situ polymerization using dibutyltin dimethoxide as initiator/catalyst. The montmorillonite was first modified with 1-decyl-2-methyl-3-(11-hydroxyundecyl)- imidazolium cation. The hydroxyl functionality was used for not only initiating polymer chains from the surface of the clay platelets but also for grafting polymer chains to the surface by acting as a reversible chain transfer …

Novel Π-Conjugated Materials Plus Their Characterizations And Applications, Xiuxian He

All Dissertations

The theme of this dissertation will focus on the syntheses and characterization of bipyridine (bipy) containing π-conjugated polymers (CPs). Specifically, poly(p-phenylene ethynylene), polyfluorene and poly(p-phenylene vinylene) derivatives have been prepared via Sonogashira coupling, Suzuki coupling and Heck coupling, respectively. Derivatives of poly(p-phenylene ethynylene), polyfluorene and poly(p-phenylene vinylene) are known to have applications in optical and electronic devices. Through this study, polymers condensed with bulky bipy-containing TAB as one of the copolymer units have shown increased solubility and diminished intrachain/interchain aggregation in solution and in film due to the effectiveness of TAB in controlling the relative orientations of individual polymer chains. …

Investigation Of Novel Quasiliving Polyisobutylene Chain-End Functionalization (Quenching) Methods, David Lee Morgan

Dissertations

This volume recounts efforts toward the development and understanding of chain functionalization techniques involving the direct addition of nucleophiles to quasiliving polyisobutylene (PIB). Nucleophiles included in the study were sterically hindered organic bases, (di)sulfides, N-substituted pyrroles, and alkoxybenzenes. A kinetic investigation of the end-quenching of TiCl4-catalyzed quasiliving PIB with sterically hindered amines was used to determine the mode of interaction with TiCl4 and the active species responsible for -proton abstraction. 2,5-disubstituted-N-hydropyrroles formed pyrrole-TiCl3 adducts that were active in formation of exo-olefin chain ends; whereas, with other sterically hindered amines, only an equilibrium fraction of the amine that did not complex …

Self-Assembly And Gold Nanoparticle Cross-Linking Of Stimuliresponsive Block Copolymers Synthesized Bt Reversible Addition-Fragmentation Chain Transfer Polymerization, Adam Eugene Smith

Dissertations

The ability of amphiphilic block copolymers to self-assemble into various morphologies in aqueous solution in response to specific stimuli has attracted widespread interest for potential applications as targeted drug delivery and diagnostic vehicles. Stimuli-responsive block copolymers afford a facile method for tuning the hydrophilic mass fraction to provide access to various solution morphologies. Reversible additionfragmentation chain transfer (RAFT) polymerization provides the ability to prepare stimuli-responsive block copolymers while maintaining precise control over the macromolecular characteristics (molecular weight, copolymer composition, functionality, etc.) that dictate nanostructure morphology.

This work may be divided into four sections. In the first section the synthesis and …

Synthesis Of Functional Copolymers Via Aqueous Raft Polymerization For Bioconjugation And Targeted Delivery Of Small Interfering Rna, Adam Wesley York

Dissertations

The versatility of reversible addition-fragmentation chain transfer (RAFT) polymerization has moved this controlled radical technique to the forefront of copolymer construction for bioapplications including polymeric drug/gene delivery vehicles. Strengths of the RAFT process include the capacity to control the polymerization of a wide variety of vinyl monomers under mild conditions, its tolerance to numerous chemical groups that allow the preparation of functional copolymers for facile modification, and the range of copolymer architectures with predetermined end group functionalities which may be synthesized. Given these strengths, RAFT polymerization was utilized in this research to synthesize functional/reactive copolymers for bioconjugation and targeted delivery …

Molecular Design And Patterning Of Biosurfaces On Poly(Tetrafluoroethylene) (Ptfe), Nattharika Aumsuwan

Dissertations

This dissertation describes the design, synthesis, and development of biocompatible poly(tetrafluoroethylene) (PTFE) surfaces that exhibit anti-microbial, anticoagulant, and dual functional surface properties. It consists of two parts: (1) design, synthesis, and analysis of antimicrobial and anti-coagulant PTFE surfaces, and (2) controllable micropatterning of anti-microbial and anti-coagulant species on the surface. PTFE was modified by Ar microwave plasma reactions in the presence of maleic anhydride, which upon hydrolysis creating COOH groups. These COOH primers were utilized as a platform for further surface reactions to attach polyethylene glycol (PEG) spacers, and penicillin (PEN) or ampicillin (AM) onto the PTFE surfaces. The use …

Nanomaterials From Biologically Active Molecules: Self-Assembly And Molecular Recognition, Min Yu

Dissertations

This dissertation describes the development of molecular assemblies and molecular recognition of phospholipids (PLs) that exhibit potential applications in emerging nanotechnologies. It consists of two parts: (1) structural features of PLs responsible for recognition of synthetic copolymers, and (2) design, synthesis and analysis of magnetic nanotubes obtained from PLs with a common theme of colloidal synthesis served as a platform for film formation and nano-assemblies of nanotubes. Poly(methyl methacrylate/n-butyl acrylate) (p-MMA/nBA) colloidal particles that were stabilized by 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) PLs were synthesized, and upon the particle coalescence, PL stratification resulted in the formation of surface localized ionic clusters (SLICs). These …

Aqueous Raft Synthesis Of Stimuli-Responsive, Amphiphilic Block Copolymers And Self-Assembly Behavior In Solution And Incorporation Into Lbl Films, Matthew Grady Kellum

Dissertations

Of all the living radical polymerization techniques, reversible addition– fragmentation chain transfer (RAFT) polymerization is arguably the most versatile in terms of the reaction conditions (e.g. temperature and solvent selection), monomer selection (e.g. neutral, anionic, cationic, and zwitterionic), and purification. Since the introduction of RAFT in 1998, the McCormick research group and others including the Lowe, Sumerlin, and Davis research groups have synthesized a wide range of (co)polymers with predetermined molecular weights, low polydispersities, and advanced architectures utilizing aqueous RAFT (ARAFT) polymerization. These research groups have also studied how various block copolymers exhibit stimuli-responsive behavior due to a change in …

Multi Stimuli-Responsive Copolymers Obtained From Colloidal Dispersions, Fang Liu

Dissertations

This dissertation describes the design, synthesis, and development of multi stimuli-responsive random copolymers that exhibit collective responsiveness to temperature, pH or electromagnetic radiation. New colloidal particles of poly(N-(DL)-(1- Hydroxyymethyl) propylmethacrylamide/n-butyl acrylate) (p(DL-HMPMA/nBA) and poly(2-(N,N′-dimethylamino)ethyl methacrylate/n-butyl acrylate) (p(DMAEMA/nBA)) were synthesized, which upon coalesce to form solid continuous films. The presence of lower glass transition (Tg) nBA components not only facilitate film formation, but also provide sufficient free volume for polymer chain rearrangements. These studies showed that coalesced films exhibit 3D dimensional changes upon external stimuli, which are attributed to the collapse and conformational changes of stimuli-responsive components as well as buckling …

Rational Design Of Self-Assembled Nanostructures Based On Polymers Synthesized Via Aqueous Reversible Addition-Fragmentation Chain Transfer Polymerization, Stacey Kirkland York

Dissertations

Recent advances in reversible addition-fragmentation chain transfer (RAFT) polymerization have allowed the rational, bottom-up design of biorelevant assemblies. Utilizing foresight, polymers can be tailored to self-assemble into nano-, micro-, and macroscopic structures. Given the size scale on which rationally-designed polymers can be tailored, they hold significant promise in the biomedical field. For example, nanoscale materials can be designed to carry small-molecule and gene therapeutics while macroscopic structures can be tailored for cell growth scaffolds. The design process begins by selecting monomers, chain transfer agents, and reaction conditions which will yield the desired polymer architecture and composition.

The work herein builds …