Chemistry Commons^™

Advancing Structure-Property Relationships In Functional Materials Via Thiol-Ene Photopolymerization, Brian Richard Donovan

Dissertations

Thiol-ene photopolymerizations provide a robust and versatile synthetic pathway to functional materials, and owing to the radical step-growth nature of polymerization and the resulting homogenous network structure, provide non-convoluted insight into how network chemistry influences and dictates macromolecular properties.

The first facet of this dissertation focuses on the design and synthesis of bio-inspired, thin film adhesives for dry and aqueous adhesion. Drawing inspiration from the intertidal marine mussel, Chapter II details the synthesis of adhesive networks containing a monofunctional catechol-based monomer. The inclusion of a catechol group resulted in significant improvements in adhesion on a variety of substrates. In Chapter …

Polymer Micelle Formulation For The Proteasome Inhibitor Drug Carfilzomib: Anticancer Efficacy And Pharmacokinetic Studies In Mice, Ji Eun Park, Se-Eun Chun, Derek Alexander Reichel, Jee Sun Min, Su-Chan Lee, Songhee Han, Gongmi Ryoo, Yunseok Oh, Shin-Hyung Park, Heon-Min Ryu, Kyung Bo Kim, Ho-Young Lee, Soo Kyung Bae, Younsoo Bae, Wooin Lee

Pharmaceutical Sciences Faculty Publications

Carfilzomib (CFZ) is a peptide epoxyketone proteasome inhibitor approved for the treatment of multiple myeloma (MM). Despite the remarkable efficacy of CFZ against MM, the clinical trials in patients with solid cancers yielded rather disappointing results with minimal clinical benefits. Rapid degradation of CFZ in vivo and its poor penetration to tumor sites are considered to be major factors limiting its efficacy against solid cancers. We previously reported that polymer micelles (PMs) composed of biodegradable block copolymers poly(ethylene glycol) (PEG) and poly(caprolactone) (PCL) can improve the metabolic stability of CFZ in vitro. Here, we prepared the CFZ-loaded PM, PEG-PCL-deoxycholic …

Thermal Conductivity Performance Of Polypropylene Composites Filled With Polydopamine-Functionalized Hexagonal Boron Nitride, Lin Chen, Hong-Fei Xu, Shao-Jian He, Yi-Hang Du, Nan-Jie Yu, Jun Lin, Sergei I. Nazarenko

Faculty Publications

Mussel-inspired approach was attempted to non-covalently functionalize the surfaces of boron nitride (BN) with self-polymerized dopamine coatings in order to reduce the interfacial thermal barrier and enhance the thermal conductivity of BN-containing composites. Compared to the polypropylene (PP) composites filled with pristine BN at the same filler content, thermal conductivity was much higher for those filled with both functionalized BN (f-BN) and maleic anhydride grafted PP (PP-g-ma) due to the improved filler dispersion and better interfacial filler-matrix compatibility, which facilitated the development of more thermal paths. Theoretical models were also applied to predict the composite thermal conductivity in which the …

Synthesis Of Alkyl Substituted Phenylated Poly(Ether Ether Ketone Ketone)S, Matthew Cerone

Browse all Theses and Dissertations

A phenylated bis(fluorobenzoyl) monomer, 5-hexyl-2,3-diphenyl-1,4-bis(fluorobenzoyl)benzene, was synthesized via a four-step process. The first three compounds synthesized were diethyl 5-hexyl-2,3-diphenyl-1,4-benzenedicarboxylate, 5-hexyl-1,4-bis(hydroxymethyl)-2,3-diphenylbenzene and 5-hexyl-2,3-diphenyl-1,4-benzenedicarboxaldehyde. The final step involved the reaction of the Grignard formed from p-bromofluorobenzene with the dialdehyde to yield a diol intermediate which was oxidized to the bis(fluorobenzoyl) monomer by use of a Jones oxidation. The monomer was polymerized by nucleophilic aromatic substitution (NAS) with bisphenol-A, resorcinol, and hydroquinone in N-methyl-pyrrolidone (NMP) to yield novel, phenylated PEEKKs. The number-average molecular weights (Mn) for the polymers were found to be 35,700 g/mol, 34,800 g/mol and 28,000 g/mol, respectively and the weight-average …

Impact Of Atmospheric Pressure Nonequilibrium Plasma Discharge On Polymer Surface Metrology, Laurence Scally, James Lalor, Patrick J. Cullen, Vladimir Milosavljevic

Articles

Due to the attraction of plasma technologies as a clean and efficient means of surface modification, significant research has gone into the physical and chemical aspects of polymer functionalization. In this study, it was shown that the use of an atmospheric plasma jet can efficiently modify the surface of polyethylene terephthalate samples and change their hydrophobic properties to more hydrophilic characteristics. The dependence on the changes with respect to time, distance, and atomic oxygen (O I) intensity were considered as factors. It was found that with closer proximity to the plasma source (without causing thermal degradation) and with increasing levels …

In-Column Polymer Modifications: Advancing Polymer Bonded Phases, Alexis G. Huckabee

Open Access Dissertations

Glycosylation is the most common post-translational modification affecting protein activities, including delivery to cell surface, binding affinity, and mediating different physiological effects. Separations of glycoproteins and their glycoforms are essential for drug discovery and development, identification of potential disease biomarkers and quality control. The efficiency of glycoprotein separations is limited by the bonded phases, requiring advances in chromatographic materials. Such advances would improve resolution, allowing for more species to be isolated from a mixture and studied.

Our group found that submicrometer nonporous silica stationary phases with tethered polymer chains (acrylamide) give excellent hydrophilic liquid chromatography (HILIC), a common method used …

Silver-Polymer Nanocomposites, Anita N. Paul

Electronic Theses and Dissertations

The objective of this research was the development of an efficient method for the preparation of silver-polymer nanocomposites containing finely dispersed silver nanoparticles. The surface of nanosilver was functionalized by thiolation with 2-aminoethanethiol. Amino-modified nanosilver was covalently bonded to polyacrylic acid, biodegradable polymers like acid terminated polylactic acid, ester terminated poly(DL-lactide-co-glycolide) and acid terminated poly(DL lactide-co-glycolide) in the presence of diisopropylcarbodiimide by carbodiimide method. Esterification of the carboxyl groups of Ag-polyacrylic acid by hydrochloric acid in methanol resulted in the formation of a stable colloidal dispersion of Ag nanoparticles in the polymer matrix. It was observed that not just acid …

To Bend Or Not To Bend – Are Heteroatom Interactions Within Conjugated Molecules Effective In Dictating Conformation And Planarity?, Gary Conboy, Howard J. Spencer, Enrico Angioni, Alexander L. Kanibolotsky, Neil J. Findlay, Simon J. Coles, Claire Wilson, Mateusz B. Pitak, Chad Risko, Veaceslav Coropceanu, Jean-Luc Brédas, Peter J. Skabara

Chemistry Faculty Publications

We consider the roles of heteroatoms (mainly nitrogen, the halogens and the chalcogens) in dictating the conformation of linear conjugated molecules and polymers through non-covalent intramolecular interactions. Whilst hydrogen bonding is a competitive and sometimes more influential interaction, we provide unambiguous evidence that heteroatoms are able to determine the conformation of such materials with reasonable predictability.

Biodegradable Copolymers Made With Magnesium Complexes, Reile M. Slattery, Joseph M. Fritsch

Seaver College Research And Scholarly Achievement Symposium

In this study, a bis-ligated magnesium complex was used to initiate the ring opening copolymerization of L-lactide (L-LA) and ϵ-caprolatone (ϵCL) and the isolated polymeric materials were characterized with NMR spectroscopy. First, the simultaneous feeding of both monomers resulted in the synthesis of homopolymer poly-lactic acid (PLA). Polymerization experiments with sequential addition of L-LA and ϵCL yielded surprising results. The ring opening polymerization of ϵCL yielded poly-caprolactone (PCL) which with the addition of L-LA yielded a di-block copolymer of PCL and PLA. The presence of the two homopolymer blocks in the copolymer was identified with ¹³C NMR where …

A 1-D Coordination Polymer Route To Catalytically Active Co@C Nanoparticles, Anand Pariyar, Siddharth Gopalakrishnan, Joseph Stansbery, Rajankumar L. Patel, Xinhua Liang, Nikolay Nikolaevich Gerasimchuk, Amitava Choudhury

Chemistry Faculty Research & Creative Works

Pyrolysis of a 1-D polymeric cobalt(ii) coordination complex ([Co(BDC)(Mim)₂]_n, H₂BDC = benzenedicarboxylic acid; Mim = N-methylimidazole) results in the formation of carbon embedded fcc cobalt nanoparticle composites, Co@C. The as-prepared Co@C shows an agglomerated secondary structure with a highly embedded carbon shell comprising of cobalt nanoparticles of 20-100 nm. These Co@C particles show excellent catalytic activity in the reduction of nitrophenol to aminophenol, studied as a model reaction, and evolves as a promising candidate for the gas phase reduction process.

Chemistry And Biochemistry News, Georgia Southern University

Biochemistry, Chemistry & Physics: News & Publications (2012-2023)

• Brawns of Brainy Polymers
• You Can't Always Eat What You Want
• Biomaterials Serves as Inspiration for the Youth
• BSL-2 Lab Unique to GSU Is Up and Running
• Polymer Coatings Program at GSU Is Opening Doors
• Professor Wins Prestigious Rising Star Award

Synthesis, Characterization, And Polymerization Of Sulfonamide Based Bifunctional Monomers, Brady Hall

Browse all Theses and Dissertations

A series of bifunctional monomers based on N,N-diallylbenzenesulfonamides with varying groups on the benzene moiety were investigated. The main goal of this project was to polymerize these monomers using radical and acyclic diene metathesis (ADMET) polymerization methods to polymerize through the allyl groups, and nucleophilic aromatic substitution (SNAr) to polymerize through the fluorine groups on the phenyl ring. Using phenyl substituted benzenesulfonyl chloride derivatives as a starting material, a series of N,N-diallylbenzenesulfonamide derivatives were prepared. The ADMET and radical cyclopolymerizations were monitored by 1H NMR spectroscopy, observing the disappearance of signals for the allyl groups in both, and the appearance …

Synthesis And Characterization Of Functionalized Poly(Arylene Ether Sulfone)S Using Click Chemistry, Kavitha Neithikunta

Browse all Theses and Dissertations

Poly(arylene ether sulfone)s with pendent aryl iodide group was successfully synthesized via Nucleophilic aromatic polycondensation of 1-(3,5-difluorophenyl sulfonyl)-4-iodobenzene using 4,4’-difluorodiphenylsulfone (DFDPS) and Bisphenol A in the ratio 25:75:100. Iodo monomer was prepared by reacting 3,5-difluorodiphenyl sulfone with N-iodo succinimide (NIS). Using GC/MS and NMR spectroscopy, the quantitative analysis was done to this monomer. Modification was done to iodo copolymer using sodium azide and copper sulfate as catalyst to form azide copolymer. Further modification of the azide copolymer to triazole copolymers via Click Chemistry using different alkynes such as 1-octyne, phenyl acetylene, propargyl alcohol and acetylenedicarboxylic acid. Polymers characterization was done …

Thermal Properties Of Poly(Arylene Ether)S Prepared From N,N-Dialkyl-2,4-Difluorobenzenesulfonamides, James Kanyoko Waweru

Browse all Theses and Dissertations

A series of poly(arylene ether)s were synthesized by nucleophilic aromatic substitution reaction (NAS) polycondensation of N,N-dialkyl-2,4-difluorobenzenesulfonamides. The aim of the project was to determine the thermal properties of poly(arylene ether)s by varying pendent sulfonamide activating group. The sulfonamide-activated monomers were synthesized by reacting 2,4-difluorobenzenesulfonyl chloride with a series of n-alkyl, iso-alkyl and cycloalkyl amines, ranging from n-propyl to n-octyl. Their poly(arylene ether)s were prepared with bisphenol-A as the nucleophilic reaction partner. The 4’-bromo-2,4-difluorodiphenylsulfone monomer, was utilized to synthesized copolymer with 4,4’-difluorodiphenylsulfone and bisphenol-A. The polymers were characterized by 1H and 13C NMR spectroscopy, TGA, DSC and SEC. Sulfonamide based polymers, …

Solution-Printed Organic Semiconductor Blends Exhibiting Transport Properties On Par With Single Crystals, Muhammad R. Niazi, Ruipeng Li, Er Qiang Li, Ahmad R. Kirmani, Maged Abdelsamie, Qingxiao Wang, Wenyang Pan, Marcia M. Payne, John E. Anthony, Detlef-M. Smilgies, Sigurdur T. Thoroddsen, Emmanuel P. Giannelis, Aram Amassian

Chemistry Faculty Publications

Solution-printed organic semiconductors have emerged in recent years as promising contenders for roll-to-roll manufacturing of electronic and optoelectronic circuits. The stringent performance requirements for organic thin-film transistors (OTFTs) in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require performance currently achieved by organic single-crystal devices, but these suffer from scale-up challenges. Here we present a new method based on blade coating of a blend of conjugated small molecules and amorphous insulating polymers to produce OTFTs with consistently excellent performance characteristics (carrier mobility as high as 6.7 cm²V⁻¹s⁻¹, low threshold …

Effect Of Surfactant Architecture On Conformational Transitions Of Conjugated Polyelectrolytes, Greg A. Braggin

Master's Theses

Water soluble conjugated polyelectrolytes (CPEs), which fall under the category of conductive polymers, possess numerous advantages over other conductive materials for the fabrication of electronic devices. Namely, the processing of water soluble conjugated polyelectrolytes into thin film electronic devices is much less costly as compared to the processing of inorganic materials. Moreover, the handling of conjugated polyelectrolytes can be performed in a much more environmentally friendly manner than in the processing of other conjugated polymers because conjugated polyelectrolytes are water soluble, whereas other polymers will only dissolve in toxic organic solvents. The processing of electronic devices containing inorganic constituents such …

Photophysics Of Organic Semiconductors: From Ensemble To The Single-Molecule Level, Rebecca Grollman, Whitney E. B. Shepherd, Alexander Robertson, Keshab R. Paudel, John E. Anthony, Oksana Ostroverkhova

Chemistry Faculty Publications

We present photophysical properties of functionalized anthradithiophene (ADT) and pentacene (Pn) derivatives, as well as charge and energy transfer properties of donor-acceptor (D/A) pairs of these derivatives. All molecules studied were fluorescent and photostable enough to be imaged on the single-molecule level in a variety of polymeric and in a functionalized benzothiophene (BTBTB) crystalline host using room-temperature wide- field epifluorescence microscopy. Flexibility of functionalization of both guest (ADT, Pn) and host (BTBTB or polymer) molecules can be used for systematic studies of nanoscale morphology and photophysics of D/A organic semiconductor bulk heterojunctions, as well as in applications relying on FRET, …

Novel Sustainable Polymers Derived From Renewable Rosin And Fatty Acids, Perry Wilbon

Theses and Dissertations

In the work of this dissertation, polymers derived from renewable bio-based resources prepared by various polymerization techniques were investigated. The properties of these polymeric materials were characterized and discussed. Rosin was first converted into acrylate or methacrylate monomers for atom transfer radical polymerization (ATRP). Second, rosin was combined with vegetable oil to produce completely renewable novel polyesters by acyclic diene metathesis (ADMET) polymerization. Third, degradable block copolymers were synthesized composed of polycaprolactone and rosin grafted polycaprolactone with the aid of ring-opening polymerization (ROP). Finally, degradable polyesters were produced using vegetable oil derivatives as starting materials. These new rosin and fatty …

A Comparative Study On Fabrication Of Cu$_{2}$Znsns$_{4}$ (Czts) Nanofibers Using Acetate And Chloride Metal Precursors, Burak Zafer Büyükbekar, Faruk Özel, Hüseyi̇n Şakalak, Hali̇t Çavuşoğlu, Mustafa Ersöz, Mahmut Kuş, Mustafa Selman Yavuz

Turkish Journal of Chemistry

This study reports, for the first time, the fabrication of electrospun Cu$_{2}$ZnSnS$_{4}$ (CZTS) nanofibers using metal acetate precursors. Viscous poly(vinyl pyrrolidone) (PVP) solution containing acetate or chloride salts of copper, zinc, and tin was electrospun onto a conductive substrate. The PVP nanofibers that have a mixture of metal salts were annealed at elevated temperatures. After calcination, these nanofibers were treated with the sulfur source and then annealed again in order to generate CZTS nanofibers. The CZTS nanofibers generated from acetate and chloride salts were characterized and compared. Belt-like and wire-like nanofibers were obtained when using metal acetate and chloride precursors, …

Initiated Chemical Vapor Deposition (Icvd) Polymer Thin Films : Structure-Property Effects On Thermal Degradation And Adhesion, Vijay Jain Bharamaiah Jeevendrakumar

Legacy Theses & Dissertations (2009 - 2024)

Opportunities and challenges for chemical vapor deposition (CVD) of polymer thin films stems from their applications in electronics, sensors, and adhesives with demands for control over film composition, conformity and stability. Initiated chemical vapor deposition (iCVD) is a subset of the CVD technique that conjoins bulk free-radical polymerization chemistry with gas-phase processing. The novelty of iCVD technique stems from the use of an initiator that can be activated at low energies (150 – 300 °C) to react with surface adsorbed monomer to form a polymer film. This reduces risk for potential unwarranted side-reactions.

Physicochemical And Structural Analysis Of Polymers As Putative Drugs, Meghan L. Thompson

Theses and Dissertations

Sulfated low molecular weight lignins (LMWLs) have shown good activity as anticoagulants by allosterically inhibiting thrombin, as well as promising agents for treating emphysema through inhibition of elastolysis, oxidation, and inflammation. Sulfated LMWLs are chemo-enzymatically synthesized from starting monomers caffeic, ferulic, and sinapic acid into sulfated dehydropolymers known as CDS, FDS, and SDS. To further the LMWLs’ development as drugs, their structural composition and physicochemical characteristics were defined in this work. The molecular weight distribution profile of the sulfated LMWLs from size exclusion chromatography performed on a high pressure liquid chromatography system (SEC-HPLC) changed from bimodal when no surfactant is …

Form Factor Of Pnipam Microgels In Overpacked States, U. Gasser, J. S. Hyatt, J.- J. Lietor-Santos, E. S. Herman, L. Andrew Lyon, A. Fernandez-Nieves

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We study the form factor of thermoresponsive microgels based on poly(N-isopropylacrylamide) at high generalized volume fractions, ζ, where the particles must shrink or interpenetrate to fit into the available space. Small-angle neutron scattering with contrast matching techniques is used to determine the particle form factor. We find that the particle size is constant up to a volume fraction roughly between random close packing and space filling. Beyond this point, the particle size decreases with increasing particle concentration; this decrease is found to occur with little interpenetration. Noteworthily, the suspensions remain liquid-like for ζ larger than 1, emphasizing the importance of …

Tandem Mass Spectrometry Of Multiply Charged Polymers: Using Ms3 Strategies For Full Structural Characterization Of Polyacrylamides, Paul M. Krauss

Williams Honors College, Honors Research Projects

In mass spectrometry, a compound is taken and converted into a gas-phase ion by an electrical charge (Balogh, 2009). From these ions, a chart is then created that displays the mass to charge ratio, which is able to then be analyzed to find out the charge of the ions, as well as the mass of the compound (Balogh, 2009). One specific type of mass spectrometry there is available is known as a fragmentation spectrometry. In fragmentation spectrometry, the molecule is not only ionized and analyzed, but fragmented parts that are formed into ions are also ionized and analyzed. This is …

The Curing And Degradation Kinetics Of Epdm Rubber, Robert J. Wehrle

Browse all Theses and Dissertations

Ethylene-propylene-diene (EPDM) rubbers containing varying amounts of diene were cured with sulfur using either a moving die rheometer (MDR) or a rubber process analyzer (RPA). The effect of removing curatives and how the curing reaction changed was explored. Kinetic data was extracted from the rheology plots and reaction rate constants were determined by two separate ways: manually choosing points of interest or by a computer model.

Synthesis And Characterization Of Manganese Pyridazyl Complexes, Sana Shah

Masters Theses & Specialist Projects

Heterocyclic’s and their fused-ring derivatives have been of interest for their use in electronic materials due to their ease of production, synthetic versatility, and low cost compared to traditional inorganic materials like silicon. Pyridazines have been found to be useful in catalysis gas storage, polymeric sensors and biological mimetics. When a transition-metal is fused into a synthesized pyridazine, unique properties such as conductivity and optics are allowed. In this work, synthesized pyridazine complexes will be analyzed by mass spectroscopy, elemental analysis, nuclear magnetic resonance, imaging, x-ray crystallography, and infrared spectroscopy. We are interested in synthesizing organometallic pyridazines and manganese pyridazyl …

Obstacles And Solutions To Studying Functional Adhesives Using Vibrational Sum-Frequency Generation Spectroscopy, Angela Renee Andersen

Theses and Dissertations

Important aspects of adhesion occur at interfaces, including structures that may be different from those in the bulk materials. However, probing the orientation of molecules in functional adhesives poses a significant challenge because adhesive molecules are always located at a buried interface. The limited penetration depth of surface-specific analysis prohibits the study of buried interfaces using those techniques. The large quantity of bulk molecules relative to the adhesive molecules interacting at the interface results in the bulk signal swamping out adhesive signal in bulk analysis techniques. An interface-specific technique is required to study functional adhesives. One such technique that has …

Design, Synthesis And Characterization Of Chain-End Functionalized Glyco-Polymer For Efficient Proteomic Analysis, Satya Nandana Narla

ETD Archive

No abstract provided.

The Enhancement Of Peroxide-Cured Fluoroelastomer Rubber To Metal Bonding, Richard Hunter Cooke Iii

Browse all Theses and Dissertations

A "combi-cured&" fluoroelastomer (FKM) rubber formulation was designed to yield 100% cohesive rubber failure when cured to cold-rolled steel with derivatives of polymeric silane adhesives. Three different categories of adhesives were tested: Unsaturated Polymeric Silane with Phosphonium Salt (UPSP-D), Unsaturated Polymeric Silane (UPS-L), and Saturated Polymeric Silane (SPS-L). Adhesion Inserts molded using ASTM Method D429 Method C all consistently yielded 100% cohesive rubber failure and showed adhesion strength in the range of 700 to 800 psi after being pulled at 2" per minute until break. After obtaining consistent 100% rubber failure, a design of experiment (DOE) was implemented to determine …

Synthesis And Characterization Of Biodegradable Poly(Vinyl Esters) With Hdac Inhibitory Activity, Kyle Lawrence Horton

Wayne State University Theses

HDAC inhibitors are known to have anti-inflammatory properties. HDAC inhibitors are used in combination with Oct4 to generate induced pluripotent stem cells. I hypothesized that polyesters based on simple aliphatic HDAC inhibitors like valproic acid (VPA) and phenylbutyric acid (PBA) can serve as alternatives to existing polyester biomaterials with improved anti-inflammatory properties and as scaffolds for generation of iPSCs when used in combination with layer-by-layer thin films delivering reprogramming transcription factors. Vinyl ester of phenylbutyric acid (VEPA) and vinyl ester of valproic acid (VEVA) were synthesized from their carboxylic acid precursors using an iridium complex catalyst at yields as high …

On Metal Synthesis Of Some Substituted Rhenium And Manganese Complexes, Jaron Michael Thomas

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (i.e. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to their non-aromatic analogs (i.e. polyacetylene). Our current interest focus upon the potential role of metal ligand bound pyridazines as the next generation of electronic devices that utilize the metal ligands bound to organics as the semiconducting material. Pyridazine is a 6-membered aromatic ring with two adjacent nitrogen atoms. These are promising candidates for a variety of materials and commercial applications; but they are difficult to get a metal ligand to fuse …