Chemistry Commons^™

Section Abstracts: Chemistry

Virginia Journal of Science

Abstracts of the Chemistry Section for the 90th Annual Meeting of the Virginia Academy of Science, May 23-25, 2012, Norfolk State University, Norfolk, Virginia.

Novel Solid State Properties Of Drugs, Polymers And Various Chemicals By Thermal And Analytical Techniques, Dhruthiman R. Mantheni

ETD Archive

I have observed unique variations in AC electrical conductivity of solids by dielectric analysis (DEA or DETA) when studied with respect to temperature and frequency. A wide range of solids were examined for this study e.g. organics, polymers, carbohydrates, API's (active pharmacy ingredients) and amino acids. Experimental results clearly show novel dielectric behavior of a linear increase in a log ionic conductivity vs. temperature in the pre-melt (20 to 30oC below the melt temperature) and melt transition regions. We have differentiated the solids which show the conductivity variations in pre-melt from those which do not e.g. pre-melt conductivity variations observed …

Polymers Used In Medicine: Common Types And Benefits Of Drug Delivery Systems, Camille Andrews

Natural Sciences Student Research Presentations

This poster describes the common types and benefits of drug delivery systems.

Photochemistry And Applications Of Diels-Alder Adducts And Photoacids In Materials Science, Valentine Johns

Electronic Theses and Dissertations

In chapter I Photo-retro-Diels-Alder (PrDA) reactions of a variety of Diels Alder (DA) adducts were studied. Experimental results showed that the photoreactivity (quantum yield) depends on the electron-donating ability of the diene component and the electronwithdrawing ability of the dienophile component. The mechanism was studied by trapping the reaction intermediate, O2 quenching and femtosecond time-resolved absorption spectroscopy. All the results support a mechanism that involves a charge-separated intermediate generated from a singlet excited state. The PrDA reaction may find applications in photoresponsive materials, photolithography, drug delivery and mechanistic research. Chapter II shows two applications of the PrDA reaction. The first, …

Synthesis And Characterization Of Linear And Branched Polylactic Acid For Use In Food Packaging Applications, Kyle C. Bentz

Master's Theses

Polylactic acid (PLA) resins of various molecular weights and molecular weight distributions were synthesized. Linear, narrow molecular weight distribution (MWD) PLA resins were synthesized, as well as resins containing both high molecular weight branched structures and low molecular weight chains and oligomers. Narrow MWD resins were synthesized for use as adhesives for corrugated paperboard and broad MWD resins were synthesized for use as a waterborne coating. PLA resins were dispersed for use as a waterborne coating. Success has been made at forming films utilizing various plasticizers and surfactants as well as polyvinyl alcohol as dispersing agents. A cold dispersion procedure …

Chemistry - Acs Certification, Daniel Hinson

Mahurin Honors College Capstone Experience/Thesis Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole, Figure 1A) and their derivatives have been of great interest for conductive polymers due to their novel properties, such as their versatile structure and ease of synthesis. In addition, these molecules have a great environmental stability compared to non-aromatic analogs (e.g. polyacetylene, Figure 1B). We have been interested in synthesizing organometallic pyridazyl (Figure 1C) complexes for polymer research. Figure 1. Structures of A–D. Pyridazyl complexes of rhenium were synthesized in three steps beginning from 1,2-diacylcyclopentadienes (aka, fulvenes, Figure 1D). Synthesis, characterization and molecular structure of [Mn(CO)3{1,2-C5H3(CC4H3ON)(CC4H3ON)}] (4A), [Re(CO)3{1,2-C5H3(CC4H3ON)(CC4H3ON)}] (4B), and their precursors are …

Dna-Inks For 3-D Printing: Dna Composites For The Rapid Prototyping Of Scaffold In Bioengineering Applications, Jimena I. Aguirre^, Ryan B. Wicker, Mireya A. Perez, Juan C. Noveron*, Juan M. Sanchez

COURI Symposium Abstracts, Spring 2011

Rapid-prototyping has become an incredible technique that manufactures three-dimensional objects with intricate complexity down to 8µm of resolution. We are developing materials that can be used by rapid-prototyping instruments to make scaffolds for bioengineering applications. Our molecular design involves the polymerization of a  (vinylbenzyl)trimethyl-ammonium chloride and DNA solution. Upon UV illumination, the composite polymerizes and forms DNA-hybrid materials.  The end result becomes a ductile transparent material with a thin cross-section. The synthesis, characterization and application of rapid prototyping will be described. Scanning Electron Microscopy (SEM), Light Scattering Detector (LDS), Nuclear Magnetic Resonance (NMR), and Infrared Spectroscopy indicate the structure, characteristics, …

Enhanced Photorefractivity In A Polymeric Composite Photosensitized With Carbon Nanotubes Grafted To A Photoconductive Polymer, Naveen Kumar Lingam, Sonali Kalghatgi, Jeffrey G. Winiarz

Chemistry Faculty Research & Creative Works

We report on the photosensitization of photorefractive (PR) polymeric composites through the inclusion of multiwalled and singlewalled carbon nanotubes (CNTs), respectively, having poly(N -vinyl carbazole) (PVK) grafted to their surfaces. The PR nature of the holographic gratings was confirmed via the asymmetric exchange of energy in a two-beam-coupling (TBC) geometry, yielding TBC gain coefficients approaching 80 cm^-1. In addition, in degenerate-four-wave- mixing experiments the prepared composites exhibited diffraction efficiencies as high as 60% and overmodulation voltages as low as ∼40 V/μm. These notable figures of merit indicate that the grafting of the PVK polymer to the various CNTs …

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.

Detection Of Quercetin Using Polymer Coated Quartz Crystal Microbalance And The Modification Of Á-Zirconium Phosphate To Develop A Sorbent For Organic Pollutant Removal, Darlington Mlambo

Dissertations (1934 -)

Sorption processes involve physical and chemical interactions of sorbents with analytes. These may involve the physical and/or chemical processes in which a substance is accumulated at an interface between two phases, or the intermixing of a substance with the matrix of a second phase. The two processes are referred to as adsorption and absorption respectively. The sorption capacities of different classes of sorbents have many potential and demonstrated applications such as sensor development, water treatment, environmental remediation and chromatographic separations. The goal of this work is to explore the sorption capacity of polymers as well as nanodimensional layered materials for …

Nano-Imprinted Thin Films Of Reactive, Azlactone-Containing Polymers: Combining Methods For The Topographic Patterning Of Cell Substrates With Opportunities For Facile Post-Fabrication Chemical Functionalization, Nathaniel J. Fredin, Ryan M. Flessner, Christopher M. Jewell, Shane L. Bechler, Maren E. Buck, David M. Lynn

Chemistry: Faculty Publications

Laser scanning confocal microscopy (LSCM) and atomic force microscopy (AFM) were used to characterize changes in nanoscale structure that occur when ultrathin polyelectrolyte multilayers (PEMs) are incubated in aqueous media. The PEMs investigated here were fabricated by the deposition of alternating layers of plasmid DNA and a hydrolytically degradable polyamine onto a precursor film composed of alternating layers of linear poly(ethylene imine) (LPEI) and sodium poly(styrene sulfonate) (SPS). Past studies of these materials in the context of gene delivery revealed transformations from a morphology that is smooth and uniform to one characterized by the formation of nanometer-scale particulate structures. We …

Physicochemical And Thermochemical Properties Of Sulfonated Poly(Etheretherketone) Electrolyte Membranes, Stephen Rhoden

Electronic Theses and Dissertations

Fuel cells have long been seen as an alternative to combustion powered and diesel powered engines and turbines. Production of energy via a fuel cell conversion method can generate up to 60% efficiency in comparison to 30% using a combustion powered engine, with low co-production of harmful side-products. The polymer electrolyte membrane (PEM) adapted for the fuel cell application is one of the main components that determines the overall efficiency. This research project was focused towards novel PEMs, such as sulfonated poly(etheretherketone) or SPEEK, which are cost-efficient and robust with high proton conductivities under hydrated conditions. The degree of sulfonation …

The Fabrication Of Polymer-Derived Sicn/Sibcn Ceramic Nanostructures And Investigation Of Their Structure-Property Relationship, Sourangsu Sarkar

Electronic Theses and Dissertations

Polymer-derived Ceramics (PDCs) represent a unique class of high-temperature stable materials synthesized directly by the thermal decomposition of polymers. This research first focuses on the fabrication of high temperature stable siliconcarbonitride (SiCN) fibers by electrospinning for ceramic matrix composite (CMC) applications. Ceraset™ VL20, a commercially available liquid cyclosilazane, was functionalized with aluminum sec-butoxide in order to be electrospinnable. The surface morphology of the electrospun fibers was investigated using the fibers produced from solvents. The electrospun fibers produced from the chloroform/N,N-dimethylformamide solutions had hierarchical structures that led to superhydrophobic surfaces. A “dry skin” model was proposed to explain the formation of …

Design And Development Of Chiral And Achiral Molecularly Imprinted Stationary Phases, Jason Paul Lejeune

LSU Doctoral Dissertations

Although the cross-linker can comprise over 80% of the polymer composition, improving the nature of the cross-linker in molecularly imprinted polymers has not been studied extensively. The goal of this research is to develop novel cross-linking monomers to either use in the One MoNomer Molecularly Imprinted Polymer system (OMNiMIP) or use in conjunction with other commercially available cross-linkers and functional monomers. Chapter 2 contains research into the understanding of the performance of a new cross-linking monomer (N, O - bismethacryloyl ethanolamine, NOBE) discovered in the Spivak Research Group. The ability of this monomer to outperform traditional two monomer systems in …

Electrical And Structural Studies Of Polyacrylonitrile (Pan) Complexed With Inorganic Salts., Khairul Bahiyah Md Isa

Student Works (2010-2019)

In the present study, polymer electrolyte films composed of polyacrylonitrile (PAN) as a host polymer, ethylene carbonate (EC) as the plasticizer and lithium triflate (LiCF3SO3) and sodium triflate (NaCF3SO3) as dopant salts were prepared by the solution cast technique. Five systems of polymer electrolytes films have been prepared; these systems are the plasticized-PAN system i.e. PAN-EC system, two salted-PAN systems i.e. PAN-LiCF3SO3 and PAN-NaCF3SO3, and two plasticized-salted PAN systems i.e. PAN-EC-LiCF3SO3 and PAN-EC-NaCF3SO3. The pure PAN film was prepared as a reference. The ionic conductivity for each system is characterized using impedance spectroscopy. The room temperature conductivity of the pure …

Temperature And Ph Responsive Polyethylenimine Systems As Potential Nonviral Gene Vectors, S. Chad Skidmore

Browse all Theses and Dissertations

Modified HPEI was used to determine if the LCST could be controlled by varying multiple variables, including: percent modification, pH, salt solution concentration, and weight percent. Two modifications were done with butylene oxide (Butox) and isobutyryl amide (IBAm). Specifically, 100% (HPEI-Butox1.00)butoxylated and 10% (HPEI-IBAm0.10), 54% (HPEI-IBAm0.54), and 70% (HPEI-IBAm0.70) amidated samples were synthesized. Additionally, HPEI-IBAm0.54 was further modified with hydroxyl ethyl groups (HPEI-IBAm0.54 Eox0.46) and ethyl groups (HPEI-IBAm0.54-Et0.44). The LCSTs of all amidated systems were below body temperature, 37 °C, at pH = 7.4. This indicates an ability of these systems to be used as a vector for gene delivery. …

A Characterization Of Caffeine Imprinted Polypyrrole Electrode, Deepika Mandadi

Masters Theses & Specialist Projects

Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, …

Compendium Of Polymer Terminology And Nomenclature: Iupac Recommendations, 2008 (Book Review), Jeffrey H. Glans

Chemistry & Physics Faculty Publications

Book review by Jeffrey Glans.

Polymer Division, International Union of Pure and Applied Chemistry. Compendium of Polymer Terminology and Nomenclature: IUPAC Recommendations, 2008. Royal Society of Chemistry, 2009.

Interface Slippage Study Between Polyamide 12 And Ethylene Butene Copolymer Melt In Capillary Extrusion, Jinhai Yang, James L. White

Faculty Publications

Extrusion of a polyamide 12 (PA12) material through a capillary die coated with an ethylene butene copolymer (EBM) was studied. The EBM coated die significantly increased the flow rates of the PA12 melt compared to a clean die at the same extrusion pressure. Introducing a maleic anhydride grafted ethylene-octene copolymer (EOM-g-MAH) into the EBM suppressed the effect. This behavior seems only explained by significant interface slippage between PA12 and EBM melts, which could be eliminated by introducing covalent chemical bonds across the interface. A mathematical analysis was carried out to calculate the interface slippage. The shear stress where slippage began …

Controlled Assembly Of Rodlike Viruses With Polymers, Tao Li, Laying Wu, Nisaraporn Suthiwangcharoen, Michael A. Bruckman, Dayton Cash, Joan S. Hudson, Soumitra Ghoshroy, Qian Wang

Faculty Publications

A practical method to assemble rodlike tobacco mosaic virus and bacteriophage M13 with polymers was developed, which afforded a 3D core–shell composite with morphological control.

Ratiometric Single-Nanoparticle Oxygen Sensors For Biological Imaging, Changfeng Wu, Barbara Bull, Kenneth Christensen, Jason Mcneill

Publications

It makes sense: Conjugated polymer nanoparticles doped with a platinum porphyrin dye exhibit bright phosphorescence that is highly sensitive to the concentration of molecular oxygen. The small size, extraordinary brightness, excellent sensitivity, and ratiometric emission, together with the demonstration of single-particle sensing and cellular uptake, indicate the potential of the nanoparticle sensors for quantitative mapping of local molecular oxygen concentration.

"One-Pot" Oligomeric A2 + B3 Approach To Branched Poly(Arylene Ether Sulfone)S: Reactivity Ratio Controlled Polycondensation, Andrea M. Elsen

Browse all Theses and Dissertations

The synthesis of fully soluble branched poly(arylene ether)s via an oligomeric A2 + B3 system, in which the A2 oligomers are generated in situ, is presented. This approach takes advantage of the significantly higher reactivity toward nucleophilic aromatic substitution reactions, NAS, of B2, 4-Fluorophenyl sulfone, relative to B3, tris(4-Fluorophenyl) phosphine oxide. The A2 oligomers were synthesized by reaction of Bisphenol-A and B2, in the presence of the B3 unit, at temperatures between 100 and 160 °C, followed by an increase in the reaction temperature to 180 °C at which point the branching unit was incorporated. The presence of branching was …

Photorefractivity In A Polymeric Composite Photosensitized With Nis Nanocrystals, Tyler M. Fears, Charles Anderson, Jeffrey G. Winiarz

Chemistry Faculty Research & Creative Works

The photorefractive performance of a polymeric composite photosensitized through the inclusion of NiS nanocrystals is described. The nanocrystals were characterized using visible-absorption spectroscopy, energy-dispersive x-ray spectroscopy, and transmission electron microscopy. We further demonstrate the ability to enhance various aspects of the composite's photorefractive performance by performing ligand exchange on the nanocrystals prior to their incorporation into the polymer composite. This procedure resulted in a lowering of the overmodulation voltage from ~70 to ~50 V/µm without affecting the maximum diffraction efficiency of ~40%. An increase in the two-beam-coupling gain coefficient was similarly observed, increasing from 38 to 79 cm−1. The photoconductivities …

A Selectivity Study On The Use Of Caffeine And Theobromine Imprinted Polypyrrole Surface Electrodes, Anil Kiran Kumar Vinjamuri

Masters Theses & Specialist Projects

Molecularly imprinted polymers (MIPs) are proving to be very effective in development of synthetic recognition systems and are of great interest to those interested in the field of sensor technology. The use of MIPs is receiving considerable interest due to the ability to prepare recognition matrices that possess high substrate selectivity and specificity. Conducting polymers (CP) have proved to be an excellent tool for the preparation of nano-structured biologically selective systems. Polypyrrole (Ppy) is one such CP that is extensively used for the construction of bioanalytical sensors. Ppy has shown great promise primarily due to its biocompatibility and thermal stability …

Semifluorinated Polymers Via Cycloaddition And Nucleophilic Addition Reactions Of Aromatic Trifluorovinylethers, Scott Iacono

All Dissertations

This dissertation encompasses the synthesis, characterization, and properties of semifluorinated polymers derived from thermal polymerization of aryl trifluorovinyl ether (TFVE) monomers. This work is divided into two parts based on the methodology of thermal polymerization using aryl TFVE monomers. The first part of this work involves the thermal [2 + 2]cyclodimerization of aryl TFVE monomers affording perfluorocyclobutyl (PFCB) aryl ether polymers. Chapter 1 provides an overview of PFCB aryl ether polymers as a next-generation class of high performance fluoropolymers that have been successfully employed for a myriad of technologies. PFCB aryl ether polymers are highly desired because of their high …

Systematic Synthesis And Study Of The Structure-Property Relationships Of Arylene Vinylene Polymers., Patrick Lynch

Doctoral

Much is known about the electronic, vibrational and steric effects resulting from the addition of differing organic functional groups as side chains, to the parent conjugated polymer. However the same cannot be said about the substitution of constituents of the polymer backbone itself. To this end a study is presented here which systematically studies the effects of naphthalene and anthracene substitution of the properties of poly phenylene vinylene (PPV) derivative conjugated polymers. The synthesis by the Witting-Horner reaction of derivatives is presented whereby the phenylene units of the PPV structure are methodically substituted by naphthylene and anthrylene units to form …

Poly(Arylene Ether)S With Truly Pendant Benzene Sulfonic Acid Groups, Mohamed Moustafa Abdellatif

Browse all Theses and Dissertations

A series of new sulfonated poly(arylene ether)s containing one sulfonic acid group, located on a pendant phenyl sulfonyl moiety, at every repeat unit was synthesized using 3-sulfonated-3', 5'-difluorophenyl Sulfone, 4, and a variety of bisphenols. A conventional nucleophilic aromatic substitution (NAS) was utilized for the homopolymerization and copolymerization reactions. Polymerization reactions of 4 in NMP at 180 °C provided the corresponding linear sulfonated poly(arylene ether)s, s-PAEs, with number average molecular weight, M_n, ranging from 10,000 to 38,000 Daltons. All of the polymers were characterized by ¹H and ¹³C NMR spectroscopy, thermogravimetric analysis (TGA), and differential scanning …

Chemical Analysis Of Polymer Blends Via Synchrotron X-Ray Tomography, Heath Alan Barnett

LSU Doctoral Dissertations

Material properties of industrial polymer blends are of great importance. X-ray tomography has been used to obtain spatial chemical information about various polymer blends. The spatial images are acquired with synchrotron X-ray tomography because of its rapidity, good spatial resolution, large field-of-view, and elemental sensitivity. The spatial absorption data acquired from X-ray tomography experiments is converted to spatial chemical information via a linear least squares fit of multi-spectral X-ray absorption data. A fiberglass-reinforced polymer blend with a new-generation flame retardant is studied with multi-energy synchrotron X-ray tomography to assess the blend homogeneity. Relative to other composite materials, this sample is …

Rheology Of Tin Fluorophosphate Glass/Polyamide 12 Hybrids In The Low Concentration Regime, Kevin Urman, Thomas Schweizer, Joshua U. Otaigbe

Faculty Publications

Phosphate glass (Pglass)/polymer hybrids are a unique material class that promises to help fulfill the growing need for new advanced materials. Rheological investigations into Pglass/polyamide 12 hybrids have shown a strong dependence on temperature and composition. Strong negative deviations from the log-additivity rule are also observed for these materials as well as a reduction in the activation energy for viscous flow. Hybrids containing < 2 vol. % Pglass are theologically simple fluids that display temperature independence in plots of storage modulus versus loss modulus. Hybrids containing >= 2 vol. % Pglass are rheologically complex and do not obey the time-temperature superposition principle. Through application of Han plots, we identified a structural change that occurs in hybrids containing >= 2 vol. % Pglass at …

A Coarse Grain Model For Dna, Thomas A. Knotts Iv, Nitin Rathore, David C. Schwartz, Juan J. De Pablo

Faculty Publications

Understanding the behavior of DNA at the molecular level is of considerable fundamental and engineering importance. While adequate representations of DNA exist at the atomic and continuum level, there is a relative lack of models capable of describing the behavior of DNA at mesoscopic length scales. We present a mesoscale model of DNA that reduces the complexity of a nucleotide to three interactions sites, one each for the phosphate, sugar, and base, thereby rendering the investigation of DNA up to a few microns in length computationally tractable. The charges on these sites are considered explicitly. The model is parametrized using …