Polymer Chemistry Commons^™

Synthesis Of Functional Chalcone Library For Use In Aza- Dipyrromethene Dye Systems, Kendal Crawley

Murray State Theses and Dissertations

Over the past decade, Aza-Bodipy dyes (ADPs), a derivative of the extensively studied BF₂-dipyrromethene (BODIPY), have become a growing field of research due to their unique photophysical properties, high yielding synthesis, and relative stability. They possess a unique spectral window of 600 to 750 nm which is the red to near-IR region, evidenced by the blue color of many of these dyes. Increasing interest in these dyes is due to this near-IR window which is important for many applications.^1-4 ADP chromophores also have a common core motif to that of phthalocyanines which allow for coordination at their …

Molecular Engineering Of Self-Immolative Polymers As Chemically Responsive Temporary Adhesives For Protective Garments, Hana J. Yarbrough

Dartmouth College Master’s Theses

The long-term goal of this thesis is to design novel chemical protective garments that both shield and sense for chemical warfare agents. The overarching hypothesis of this work is that joining textiles with a chemically responsive temporary adhesive will reduce the permeability of and detect hazardous analytes across fabric boundaries. Work towards achieving this goal and testing this hypothesis is separated into two chapters. The first chapter reports the development of a self-immolative polymer, poly(phthalaldehyde), into a stimuli-responsive temporary adhesive. Developing poly(phthalaldehyde) as a robust adhesive that rapidly releases substrates would be a significant and novel contribution to the fields …

Poly(Β-Gal-Thr): A New Scalable Synthetic Mucin, Manuel A. Lema

Dissertations and Theses

A method for the preparation of glycosylated polypeptides via the nucleophilic ring-opening polymerization of a glycosylated N-carboxyanhydride (NCA) monomer is reported. The synthesis of 2,3,4,6-tetraacetyl-β-galactose-threonine N-carboxyanhydride (β-AcO-Gal-Thr-NCA) monomer in 5 steps with an 8 % overall yield is described, and the single-crystal X-ray structure is provided. The effect of a series of Ni⁰-based organometallic initiators, nucleophilic amine initiators, co-catalysts, and solvents on the polymerization were explored. The kinetics of the three most promising conditions were studied in greater detail. The conditions that provided the highest yield, low polydispersity (Ð), and …

Synthesis And Characterization Of Chitosan Derivatives Intended For Gene Delivery Applications, Alex M. Mcmullen

Graduate Theses/Dissertations

Chitosan has been studied as a non-viral vector capable of efficient gene delivery due to its favorable properties such as biodegradability, biocompatibility, and is non-toxic to mammalian cells. Incorporating electrostatic interactions in non-viral vectors enhance the vector permeability. This work focuses on two parts. Firstly, cationic chitosan derivatives were synthesized using quarternary ammonium and phosphonium groups. This was achieved by coupling carboxylic acid ligands with these quarternary groups to chitosan through an amide bond. The carboxylic acid ligands were synthesized from 4-methylbenzoic acid and either triethyl phosphine or triethyl amine. The ligand was then attached to chitosan through an amide …

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 …

Enhanced Platinum (Ii) Drug Delivery For Anti-Cancer Therapy, Marek T. Wlodarczyk

Dissertations, Theses, and Capstone Projects

Over the years, anti-cancer therapies have improved the overall survival rate of patients. Nevertheless, the traditional free drug therapies still suffer from side effects and systemic toxicity, resulting in low drug dosages in the clinic. This often leads to suboptimal drug concentrations reaching cancer cells, contributing to treatment failure and drug resistance. Among available anti-cancer therapies, metallodrugs are of great interest. Platinum (II)-based agents are highly potent and are used to treat many cancers, including ovarian cancer (OC). Cisplatin (cis-diaminedichloroplatinum (II)) is the first Food and Drug Administration (FDA)-approved metallodrug for treatment of solid tumors, and its mechanism …

Tools And Strategies For The Patterning Of Bioactive Molecules And Macromolecules, Daniel J. Valles

Dissertations, Theses, and Capstone Projects

Hypersurface Photolithography (HP) is a printing method for fabricating structures and patterns composed of soft materials bound to solid surfaces and with ~1 micrometer resolution in the x, y, and z dimensions. This platform leverages benign, low intensity light to perform photochemical surface reactions with spatial and temporal control of irradiation, and, as a result, is particularly useful for patterning delicate organic and biological material. In particular, surface- initiated controlled radical polymerizations can be leveraged to create arbitrary polymer and block- copolymer brush patterns. Chapter 1 will review the advances in instrumentation architectures from our group that have made these …

Immobilized-Enzyme Reactors Integrated Into Analytical Platforms: Recent Advances And Challenges, Bert Wouters Dr, Sinead Currivan, Noor Abdulhussain, T. Hankemeier, Peter J. Schoenmakers

Articles

Immobilized-enzyme reactors (IMERs) are flow-through devices containing enzymes that are physically confined or localized with retention of their catalytic activities. IMERs can be used repeatedly and continuously and have been applied for (bio)polymer degradation, proteomics, biomarker discovery, inhibitor screening, and detection. Online integration of IMERs with analytical instrumentation, such as high-performance liquid chromatography (HPLC) systems, reduces the time needed for multi-step workflows, reduces the need for sample handling, and enables automation. However, online integration can also be challenging, as reaching its full potential requires complex instrumental setups and experienced users. This review aims to provide an assessment of recent advances …

Synthesis Of The Diazonium Zwitterionic Polymer/Monomer For Use As The Electrolyte In Polymer Electrolyte Membrane (Pem) Fuel Cells, Josiah Marshall

Electronic Theses and Dissertations

My research goals are to synthesize new zwitterionic perfluorosulfonimide (PFSI) monomer/polymers. They are expected to replace traditionally used perfluorosulfonic acid (PFSA) polymers as the electrolyte in PEM fuel cells. For the PFSI monomer preparation, we designed a nine-step synthesis route. Thus far, I have successfully completed the synthesis of 4- (2-bromotetrafluoroethoxy)-benzenesulfonyl amide, 4-acetoxybenzenesulfonic acid sodium salt, and 4-chlorosulfonyl phenyl acetate. The coupling reaction of 4-(2-bromotetrafluoroethoxy)- benzenesulfonyl amide with 4-chlorosulfonyl phenyl acetate, was troublesome due to slow reaction kinetics and byproducts. Additionally, I did a methodology study for the homopolymerziation of the perfluoro 3(oxapent-4-ene) sulfonyl fluoride monomer. We compared the weight …

Design Of Antioxidant Monomer, Augustine Osilamah Yusuf

Masters Theses & Specialist Projects

Reactive oxygen species such as hydrogen peroxide are present at the sites of inflammation in the body. Degradable polymeric nanoparticles have shown great promise in a range of biomedical applications which include preferential delivery of therapeutics to such inflamed sites. We are working towards a new class of materials expected to have tunable degradation rates in the presence of hydrogen peroxide. These new materials consist of three parts: degradable linkages, antioxidant groups, and unreactive filler monomers such as methylmethacrylate. We have synthesized a polymerization initiator with a degradable linkage, and we have shown that using this initiator to synthesize another …

Pressure Driven Desalination Membranes: Lyotropic Liquid Crystals Containing Single Walled Carbon, Matteo A. Del Giudice, Samantha Castillo Merigold

Materials Engineering

This project presents a potential alternative desalination technique that utilizes the ion rejection properties of single walled carbon nanotubes dispersed in a lyotropic liquid crystal (LLC) matrix. Previous research has pointed to the polymerizable surfactant methacryloxy ethyl hexadecyl dimethyl ammonium bromide (C16MA) having capabilities of filtering molecular components smaller than a nanometer, when oriented in cylindrical micelles. SWCNTs were dispersed in deionized water by probe sonication and addition of surfactant cetyltrimethylammonium bromide (CTAB) due to SWCNTs’ hydrophobic properties. Membranes were produced containing 55wt% C16MA, 37wt% DI water, 0.1wt% with respect to the monomer (WRM) SWCNTs, 1.9 wt% WRM 2,2-dimethoxy-2-phenylacetophenone (photointiator), …

The Emerging Applications Of Sulfur (Vi) Fluorides In Catalysis, Nicholas Ball, Cayo Lee, Jonathan E. Elisabeth, Nathan C. Friede, Glenn M. Sammis

Pomona Faculty Publications and Research

The past decade has witnessed remarkable growth of catalytic transformations in organic sulfur(VI) fluoride chemistry. This Perspective concentrates exclusively on foundational examples that utilize catalytic strategies to synthesize and react S(VI) fluorides. Key mechanistic studies that aim to provide insight toward future catalytic systems are emphasized.

Elucidation Of Optoelectronic Properties Of Pyrrolo[3,2-B]Pyrrole Chromophores, Ryan Faddis

Symposium of Student Scholars

Ryan Faddis Abstract

Elucidation of Optoelectric Properties of Pyrrolo[3,2-b]pyrrole Chromophores

Ryan Faddis and Graham S. Collier

Department of Chemistry and Biochemistry

Kennesaw State University

Derivatives of phenyl substituted pyrrolo[3,2-b]pyrroles have shown promise of being useful organic opto-electric compounds due to their advantageous tunability through careful synthetic design. Furthermore, one pot synthesis and readily accessible commercial reactants such as, aromatic amines and aldehydes, makes these molecules more favorable than other, more complex syntheses traditionally required for optically active organic molecules. Although relatively simple synthesize, more information from experimentation is needed to understand the optical properties of these species, and thus, a …

End Group Modification Of Linear Dendritic Block Copolymers (Ldbcs), Chinwe Udemgba

Honors Theses

Linear dendritic block copolymers are amphiphilic molecules that consist of a dendritic hydrophilic portion and a linear hydrophobic portion. Its unique ability to self-assemble into spherical nanoaggregates while having the potential to uptake and transport both hydrophilic and hydrophobic drugs makes these polymers an item of interest in regard to the drug delivery field. The synthesis of polyamidoamine-polylactide linear dendritic block copolymers was designed to address the common issues in drug delivery systems, including problems in permeability, solubility, stability, specificity, and retention. Though this linear dendritic block copolymer has previously been synthesized in our lab with cationic amine surface functionalities, …

Thermal, Mechanical, And Rehealing Properties Of Cross-Linked Ionene Networks, Katelyn Lindenmeyer

Honors College Theses

Polymers which contain ionic liquid groups have numerous applications in a wide variety of fields. Past research from our group has shown that IL-containing polymers which exist in covalently crosslinked networks can exhibit good ionic conductivities despite the hindrance in polymer chain mobility and relaxation. In part one of this thesis, efforts to create ionic networks which have the capability of being rehealed after exposure to an external stimulus are discussed. Thermoreversible maleimide-furan chemistry was incorporated into an imidazolium-containing ionene network. Maleimide-terminated, imidazolium-containing monomers were coupled with furan-functionalized monomers, prepared from commercially available multifunctional acrylates. Thermal, mechanical and rheological characterization …

Nitro Group Reduction For Use In Organic, Cathodic Materials, Brock G. Goeden

Honors Thesis

The industrial demand for higher capacity, light-weight battery materials has skyrocketed in recent years due to heavy investments in portable electronics, electronic vehicles, and renewable energy sources. However, rechargeable battery technology has seen little improvement since the invention of the Lithium-Ion battery in the 1980s. The low energy density of the traditionally utilized LiCoO2 cathodic material (specific capacity: 272 mAh g-1), has limited its potential to meet these increasing demands. To solve this problem, our research group is investigating new types of lightweight, organic, polymeric materials with conductive backbones as a possible replacement for the cathodic materials in Lithium-Ion batteries. …

Hydroamidation With Acetamides And Trifluoroacetamides, Gordon H. Whitetree

College of Graduate Studies: Theses & Dissertations

The hydroamidation reaction is an attractive methodology for the construction of larger functional molecules. In our research, a baseline reactivity was established for the hydroamidation reaction using a set of N-alkyl and N-aryl (trifluoro)acetamides with methyl acrylate and acrylonitrile, various bases and varying reaction conditions. The combination of alkenes, acetamides, and trifluoroacetamides with base was crucial for reaction rate. N-aryl trifluoroacetamides exhibited near quantitative conversions in neat alkene with Diazabicycloundecene (DBU) as base. The less acidic N-aryl acetamides performed much faster in the presence of KOtBu and conversions of >95% were accomplished regularly but contained a large presence …

Advancements In Bio-Based Novel (Co)Monomers For Polymeric Materials, Khristal Anne Monroe

College of Graduate Studies: Theses & Dissertations

Most current research in the area of sustainable and environmentally friendly materials relate to the use of renewable sources for the fabrication of bio-based polymers and composites. Using plant-based derivatives is a common strategy. Pine sap can be distilled into turpentines (light fraction) and pine rosin (heavy fraction). Pine rosin is obtained as a brittle solid and its major component is abietic acid. This project aims at investigating a synthetic approach for the synthesis of a pine rosin-based polymer that can be potentially used for manufacturing a collection device for pine sap. The synthetic strategy consisted in the preparation of …

Aggregation And Degradation Of Dispersants And Oil By Microbial Exopolymers (Addomex): Toward A Synthesis Of Processes And Pathways Of Marine Oil Snow Formation In Determining The Fate Of Hydrocarbons, Antonietta Quigg, Peter H. Santschi, Chen Xu, Kai Ziervogel, Manoj Kamalanathan, Wei-Chun Chin, Adrian B. Burd, Andrew Wozniak, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Microbes (bacteria, phytoplankton) in the ocean are responsible for the copious production of exopolymeric substances (EPS) that include transparent exopolymeric particles. These materials act as a matrix to form marine snow. After the Deepwater Horizon oil spill, marine oil snow (MOS) formed in massive quantities and influenced the fate and transport of oil in the ocean. The processes and pathways of MOS formation require further elucidation to be better understood, in particular we need to better understand how dispersants affect aggregation and degradation of oil. Toward that end, recent work has characterized EPS as a function of microbial community and …

Pressure Driven Desalination Utilizing Nanomaterials, Fangyou Xie

Master's Theses

Nanomaterials such as graphene oxide and carbon nanotubes, have demonstrated excellent properties for membrane desalination, including decrease of maintenance, increase of flux rate, simple solution casting, and impressive chemical inertness. Here, two projects are studied to investigate nanocarbon based membrane desalination. The first project is to prepare hybrid membranes with amyloid fibrils intercalated with graphene oxide sheets. The addition of protein amyloid fibrils expands the interlayer spacing between graphene oxide nanosheets and introduces additional functional groups in the diffusion pathways, resulting in increase of flux rate and rejection rate for the organic dyes. Amyloid fibrils also provide structural assistance to …

(Pseudo)Phase Tuning In The Service Of Synthesis: Technologies For Sustainable Catalysis., Justin Douglas Smith

Electronic Theses and Dissertations

Strategies for manipulation of chemical phases were explored with emphasis on synthetic chemistry applications. Some strategies are fairly divergent from their origin, but all ultimately began from investigations of micellar media. Accordingly, Chapter 1 reviews the historical development of micellar catalytic processes. Chapters 2 and 3 detail development of synthetic methods in micellar solutions of designer surfactant PS-750-M. PS-750-M was designed to create benign micellar solutions which effectively mimic toxic organic solvents; it contains a proline-based linker between its hydrophobic and hydrophilic regions which imparts increased polarity to the micellar core. Chapter 2 details an interfacial nucleophilic substitution of perfluoroarenes …

Visualization Without Vision – How Blind And Visually Impaired Students And Researchers Engage With Molecular Structures, Croix J. Laconsay, Henry B. Wedler, Dean J. Tantillo

Journal of Science Education for Students with Disabilities

This article examines the tools and techniques currently available that enable blind and visually impaired (BVI) individuals to visualize three-dimensional objects used in learning chemistry concepts. How BVI individuals engage with and visualize molecular structure is discussed and recent tactile (or haptic) and auditory methods for visualization of various chemistry concepts are summarized. Remaining challenges for chemistry education researchers are described with the aim of highlighting the potential value of educational research in further enabling BVI students to pursue careers in science, technology, engineering, and mathematics (STEM) fields.

I. Non-Degradable Polysiloxane Networks For Controlled Release Applications, And Ii. Additive Free, Degradable Silyl-Ether Furyl-Maleimide Networks, Caleb M. Bunton

Chemistry Theses and Dissertations

I. Two different series of non–degradable polysiloxane networks were prepared for the encapsulation and controlled release of a small molecule agent. For the first series, hydrosilylation was utilized to prepare networks of varying crosslink densities, as determined from swelling studies, from vinyl terminated and silylhydride functional poly(dimethyl)siloxanes. For the second series, the thiol-ene reaction was utilized to prepare networks of varying crosslink densities, as determined from swelling studies, from vinyl terminated and mercaptopropyl functional poly(dimethyl)siloxanes. Nile red dye was used as an encapsulated agent and dye release from each series of networks was measured using UV–vis spectroscopy to determine controllability …

Mesoporous Adsorbents For Perfluorinated Compounds, Bertha Lotsi

Electronic Theses and Dissertations

Effective adsorbents for polyfluorinated compounds (PFCs) were successfully prepared. And they were tested in the adsorption of perfluorooctanoic and perfluorooctanesulfonic acids. Bridged silsesquioxanes containing secondary and tertiary amino groups were synthesized by sol-gel condensation of bis[3-(trimethoxysilyl)propyl]amine and bis[3-(methylamino)propyl]-trimethoxysilane in acidic media with surfactants. Obtained materials are mesoporous with a high BET surface area. They combine high structural stability with a high concentration of surface amino groups serving as adsorption sites. Batch adsorption tests demonstrated their extremely high adsorption capacity on PFCs: in some experiments, it reached up to 88% of the adsorbent weight. Adsorption of PFCs changed the surfaces of …

The Synthesis Of Urethane Acrylate Resin From Palm Fatty Acid Distillate And Some Mechanical Properties, Kim Teck Teo

Student Works (2020-2029)

Depletion of petroleum reserves and increasing environmental concerns have stimulated the efforts to explore materials from readily available, renewable natural resources, such as carbohydrates, oils, fats and proteins. Plant oil and its fatty acids are promising renewable resources to produce environmentally friendly polymeric materials. Palm oil is a major crop in Malaysia and consequently palm fatty acid distillate (PFAD) has been an abundant by-product during the refinery process. PFAD could be a renewable raw material for industrial application. Thus, we develop new PFAD-based acrylate resins UV curable for coatings applications. The resins could be produced by two approaches. Firstly, mixtures …

Redox-Active Porous Organic Materials For Electrochemical Energy Storage Applications, K. Shamara Weeraratne

Theses and Dissertations

As the demand for renewable energy technologies grows, so does the need for cheaper, more efficient rechargeable batteries to store the energy. While lithium-ion battery (LIBs) technology is well established, it suffers from limited lithium supplies. Furthermore, the highly toxic transition metals used in the electrodes places a huge burden on the environment. Therefore, replacing lithium with more economical sodium metal in rechargeable batteries (i.e. sodium-ion batteries, SIBs) has garnered considerable attention. Despite the fact that sodium and lithium share similar electrochemical properties, which may cause the transition from lithium to sodium easier, the larger ionic radius of Na^{+ …}

Synthesis Of Bio-Based Polymer Products, Joshua Sukie

Williams Honors College, Honors Research Projects

The project covers the synthesis of two bio-based polymers. One aspect of the research investigates the synthesis of materials for use in vegetable oil-based UV-curable coating, and the subsequent polymerization of the materials into a coating film. The second aspect of the research follows the synthesis of a functionalized cellulose material for use as a reinforcer in a vegetable oil-based composite. Both products are subsequently analyzed by various methods.

Filtration Apparatus Design For Oil-Water Separation Using Membranes And Sponges, Alec Jerger

Williams Honors College, Honors Research Projects

It can be difficult to separate water and oil emulsions through traditional filtration. Therefore, investigations of filtering using thermo-responsive (TR) polymers, in this case poly(vinyl methyl ether) (PVME), was conducted. It’s hypothesized that below its lower critical solution temperature (LCST), PVME has an affinity for water while oil substances do not. Above the LCST the opposite will be true. To verify this hypothesis, iterations of filtration designs were created to provide optimum control over the parameters to measure flow. The final optimized experimental apparatus was a Chromaflex glass column which was air tight and controlled all parameters besides fluid flow. …

A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi

Theses and Dissertations--Physics and Astronomy

Applications of organic electronics have increased significantly over the past two decades. Organic semiconductors (OSC) can be used in mechanically flexible devices with potentially lower cost of fabrication than their inorganic counterparts, yet in many cases organic semiconductor-based devices suffer from lower performance and stability. Investigating the doping mechanism, charge transport, and charge transfer in such materials will allow us to address the parameters that limit performance and potentially resolve them. In this dissertation, organic materials are used in three different device structures to investigate charge transport and charge transfer. Chemically doped π-conjugated polymers are promising materials to be used …

Hypervalent Iodine Compounds With Carboxylate And Tetrazolate Ligands, Avichal Vaish

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ³-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL₂ (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu^-) to form ArINu₂. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, …