Chemistry Commons^™

Facile Method For Large Scale Alignment Of One Dimensional Nanoparticles And Its Biomedical Application, Sheng Feng

Theses and Dissertations

Topographical cues can profoundly affect cellular behaviors. This thesis investigate how to utilize the topographical cues generated by two techniques, flow assembly and electrospinning, to regulate cellular behaviors.

First of all, a facile and robust method to align one-dimensional (1D) nanoparticles (NPs) in large scale has been developed. Using flow assembly, representative rod-like nanoparticles, including tobacco mosaic virus (TMV), gold nanorods and bacteriophage M13, have been aligned inside capillaries by controlling flow rate and substrate surface properties. The properties of 1D NPs, such as stiffness and aspect ratio, play a critical role in the alignment. Furthermore, these hierarchically organized structures …

Impact Of Ocean Acidification On Aphotic Biogeochemical Production Of Reactive Oxygen Species, Sarah Ann Murphy

Theses and Dissertations

Reactive oxygen species (ROS) are critical to global maintenance of the global organic carbon cycle, sulfur cycle, oxygen cycle, and transition metal cycles. The primary source of ROS is commonly considered to be photolysis or photochemically driven reactions, however ROS also exist in aphotic zones. A geochemical mechanism for the same in dark environments based on the tidally driven, episodic movement of anoxic groundwaters through oxidized, Fe(III) rich sediments is shown. Predictive models were developed based on in vitro experiments and tested using sediment samples collected from a saline tidal creek in the estuary at Murrell’s Inlet, South Carolina. These …

Applications Of Organic Probes For Imaging And Analysis Of Different Cancer Cell Models, Hong Guan

Theses and Dissertations

Novel techniques for better studying cancer cell behavior and progression are extremely important. Our lab is interested in synthesizing specifically designed organic reagents and applying them in the studies of cancers. In this dissertation, we used organic probes to investigate cancer cells in the following topics: determination of amino acid concentration in different types of cancers, tumor toxicity of organic probes towards HER2 positive breast cancer cells, glycoproteins identification in breast cancer cells and development of enzyme activity assay for colon cancer cells.

The first chapter was focused on the determination of cysteine/homocysteine concentrations using turn-on sensors in cancer cells. …

Metals On Titania/Hopg As Models For Heterogeneous Catalysts, Randima Piyumalie Galhenage

Theses and Dissertations

The work done in this thesis is mainly focused on understanding the nanoscale morphology and activity of model heterogeneous catalysts. In order to do this we design and prepare model catalytic surfaces in ultrahigh vacuum (UHV) and study these surfaces using electron and ion based microscopies and spectroscopies. The nucleation, growth and chemical activity of mono and bimetallic clusters on TiO₂(110) were investigated in order to understand how activity is influenced by cluster sizes, interactions with the oxide support and surface compositions of the bimetallic clusters. For example, Au-based and Pt-based bimetallic clusters such as Co-Au, Co-Pt, and …

Tempo-Containing Romp Polymers As A Component For Treatment Of Traumatic Brain Injuries, Cameron H. Feriante

Honors College Theses

During a traumatic brain injury (TBI) sustained in combination with hemorrhagic shock the brain undergoes anoxic conditions resulting from swelling and blood loss. Traditional intravenous solutions are used to replace blood volume, but are unable to replace the blood’s oxygen carrying capacity. A proposed treatment based on isotonic solutions containing hemoglobin-based oxygen carriers (HBOC’s) which were intended to provide readily available oxygen was developed. However, cell-free hemoglobin was shown to have excessive oxidative potential. Polynitroxylated Pegylated Hemoglobin (PNPH) was developed to address this shortcoming. During PNPH synthesis a combination of polyethylene glycol (PEG) and (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), is bound to the …

Asymmetric Lipid Membranes: Towards More Realistic Model Systems, Drew Marquardt, Barbara Geier, Georg Pabst

Chemistry and Biochemistry Publications

Despite the ubiquity of transbilayer asymmetry in natural cell membranes, the vast majority of existing research has utilized chemically well-defined symmetric liposomes, where the inner and outer bilayer leaflets have the same composition. Here, we review various aspects of asymmetry in nature and in model systems in anticipation for the next phase of model membrane studies.

A Review On The Bulk And Surface Chemistry Of Iron In Atmospherically-Relevant Systems Containing Humic Like Substances (Hulis), Hind A. Al-Abadleh

Chemistry Faculty Publications

As the fourth most abundant element by mass in the Earth’s crust, iron is ubiquitous and its chemistry is rich and interdisciplinary in nature. This review synthesizes the current state of knowledge of iron chemistry in multicomponent atmospheric aerosols, which is also applicable to other atmospherically-relevant systems that include iron-containing anthropogenic nanodust, ocean surfaces and buildings. Because of the abundance of humic-like substances (HULIS) in these systems, studies on their chemistry with iron and those used as models for HULIS are the focus of this review. Findings from field measurements and laboratory studies are summarized to highlight major themes in …

The Effect Of Extended Π-Conjugation On The Spectroscopic And Electrochemical Properties Of Boron Difluoride Formazanate Complexes, Stephanie M. Barbon, Viktor N. Staroverov, Joe Gilroy

Chemistry Publications

The effect of extended π-conjugation on the spectroscopic and electrochemical properties of boron difluoride (BF₂) formazanate complexes was studied by the systematic comparison of phenyl- and naphthyl-substituted derivatives. Each of the BF₂ complexes described was characterized by ¹H, ¹³C, ¹¹B and ¹⁹F NMR spectroscopy, cyclic voltammetry, infrared spectroscopy, UV-vis absorption and emission spectroscopy and mass spectrometry. X-ray crystallography and electronic structure calculations were used to rationalize the trends observed, including direct comparison of 3-cyano-, 3-nitro- and 3-phenyl-substituted BF₂ formazanate complexes. In all cases, the wavelength of maximum absorption and emission were red-shifted …

Molecular Characterization Of Free Tropospheric Aerosol Collected At The Pico Mountain Observatory: A Case Study With A Long-Range Transported Biomass Burning Plume, K. Dzepina, C. Mazzoleni, Paulo Fialho, Swarup China, B. Zhang, R. C. Owen, D. Helmig, D. Helmig, S. Kumar, Judith Perlinger, L. Kramer, M. P. Dziobak, M. T. Ampadu, S. Olsen, D. J. Wuebbles, Lynn Mazzoleni

Department of Chemistry Publications

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m−3. On average, organic aerosol components represent the largest mass fraction of the total measured …

Improvement Of Mechanical Properties And Water Stability Of Vegetable Protein Based Plastics, Gowrishankar Srinivasan

Gowrishankar Srinivasan

Bio-renewable bio-degradable plastics are a potential solution to the growing problems of pollution caused by petroleum plastics and dependency on foreign nations for petroleum resources. One possible feed stock for these materials are vegetable proteins, especially from soy bean and corn. These proteins have relatively high molecular weights and have the potential of being processed with standard polymer processing technologies. But some issues that need to be addressed are their water instability (soy protein) and inferior mechanical properties as compared to petroleum derived plastics. In this study, soy protein isolates (SPI) and zein protein was processed with various additives and …

Investigating The Effects That Dipole Moments, Atomic Partial Charges, Vibrational Coupling, And The Potential Energy Function Have On The Hno Molecule (Nitroxyl), James Roger Smith

Chancellor’s Honors Program Projects

No abstract provided.

Microfluidic Syntheses Of Pet Radiotracers Via Fluorodenitration, Thomas Madison Moore

Doctoral Dissertations

This research study is focused on the syntheses of radiotracers for use in positron emission tomography [PET] via fluorodenitration and fluorodehalogenation under microfluidic conditions. Methodology has been developed for radiolabeling via fluorodenitration under microfluidic conditions and comparisons made to dehalogenation reactions. Developmental work was carried out on commercially available compounds containing a variety of functional groups. Subsequent production of radiotracers has been performed with precursors provided by collaborators as well as those synthesized in our laboratory.

Synthesis And Characterization Of Support-Modified Nanoparticle-Based Catalysts And Mixed Oxide Catalysts For Low Temperature Co Oxidation, Andrew Justin Binder

Doctoral Dissertations

Heterogeneous catalysts are responsible for billions of dollars of industrial output and have a profound, if often understated, effect on our everyday lives. New catalyst technologies and methods to enhance existing catalysts are essential to meeting consumer demands and overcoming environmental concerns. This dissertation focuses on the development of catalysts for low temperature carbon monoxide oxidation. CO [carbon monoxide] oxidation is often used as a probe reaction to test overall oxidation activity of a given catalyst and is an important reaction in the elimination of toxic pollutants from automotive exhaust streams. The work included here presents three new heterogeneous catalysts …

Studies Of Metalloporphyrins And Tantalum Amide Imide Compounds, Seth Carlton Hunter

Doctoral Dissertations

The focus of this dissertation is on two different subjects. The first examines the magnetic and structural properties of metalloporphyrins. In these studies, neutrons were used to probe the magnetic properties of metalloporphyrins. Insight on the structural properties of metalloporphyrins was also gained by examining the intermolecular interactions in the solid state. The second subject is the synthesis and characterization of new tantalum complexes and studies of their reactions with O₂ [dioxygen]. These complexes are potential precursors to make metal oxide and metal nitride thin films.

In the first part of this dissertation, the zero-field parameters D have been …

An Investigation Of Inorganic Compound Scattering., Karl Jay Bernstein

Doctoral Dissertations

Raman and its associated forms of spectroscopy are powerful tools that have been under-utilized. Presented within are three inorganic compounds studied with some form of Raman spectroscopy: normal Raman, hyper-Raman (HR), surface-enhanced Raman spectroscopy (SERS), surface-enhanced hyper-Raman spectroscopy (SEHRS), or resonance Raman spectroscopy (RR).

The first study involves the investigation of phosphine binding with silver metal. Phosphines find wide use in synthetic circles yet have had little study into their method of binding, unlike similar compounds comprised of sulfur. In order to understand the binding of phosphines, several tertiary phosphines, secondary phosphines and secondary phosphine oxides are examined with SERS. …

Oxygen Reduction Reaction By Copper Complex Based Electrocatalysts, Congling Zhang

Doctoral Dissertations

My research focuses on catalysis of oxygen reduction reaction (ORR) by a series of Cu(II) [copper with positive two valence] -1,2,4-triazole complex-based electrocatalysts at the cathode of PEMFC (polymer electrolyte membrane fuel cell), an efficient and environmental friendly energy conversion system compared to internal combustion engines in use today. The sluggish kinetics of ORR considerably limited the performance of PEMFCs. Understanding of ORR mechanism is important for developing affordable, active and durable ORR catalysts for such devices.

The first part of my work focused on improving the ORR performance of Cu(II)-1,2,4-triazole complex-based catalysts in an acidic environment by exploring synthesis …

The Fabrication Of Micro- And Nano- Scale Deterministic And Stochastic Pillar Arrays For Planar Separations, Teresa Byers Kirchner

Doctoral Dissertations

Planar chromatography, unlike high performance liquid chromatography (HPLC), has not experienced a significant evolution in stationary phase media since the development of the technique. This has lead HPLC to become a much more popular and robust analytical method. Main factors that contribute to improved performance of chromatographic systems include a reduction in particle size, homogeneity of the stationary phase, and an increase in velocity of the mobile phase. In general, a reduction in particle size should lead to an improvement in the performance of all chromatography systems. However, the main obstacle of improving the performance of planar chromatography systems is …

Development And Demonstration Of Critical Components Of Aluminum Based Energy Storage Devices Using The Chloroaluminate Ionic Liquids, Mengqi Zhang

Doctoral Dissertations

This dissertation considers the development of porous carbon materials as the substrates for Al deposition/dissolution in an Al based ionic liquid flow battery (ILFB) and demonstration of an Al based hybrid supercapacitor. The Aluminum chloride/ 1-ethyl-3-methylimidazolium chloride chloroaluminate ionic liquid is utilized as the electrolyte for these Al based energy storage devices. The ILFB has less capital cost than the all-vanadium redox flow battery because of the inexpensive AlCl₃. The feasibility to equip a tank of solid aluminum chloride in an ILFB system aiming to improve energy density is investigated. A critical range of temperature data (50-130 celsius …

Computational Electrodynamics And Second Hyper-Raman Scattering, Philip Dwaine Simmons Jr.

Doctoral Dissertations

Surface-enhanced second hyper-Raman spectroscopy is a type of nonlinear light scattering in which three photons are simultaneously annihilated to produce one photon whose color is slightly shifted from its third harmonic. This process, while incredibly weak, can be magnified by many orders of magnitude with the aid of plasmonic substrates. In this dissertation, three different studies are presented probing both the nature of plasmonics and nonlinear Raman scattering. In the first, nanoparticle aggregates were dosed with two isotopologues of Rhodamine 6G to determine single-molecule activity. Plasmon maps of the aggregates were then generated from electron energy-loss spectroscopy (EELS) and 3D …

Bh2 Revisited: New, Extensive Measurements Of Laser-Induced Fluorescence Transitions And Ab Initio Calculations Of Near-Spectroscopic Accuracy, Fumie X. Sunahori, Mohammed Gharaibeh, Dennis J. Clouthier, Riccardo Tarroni

Chemistry Faculty Publications

The spectroscopy of gas phase BH₂ has not been explored experimentally since the pioneering study of Herzberg and Johns in 1967. In the present work, laser-induced fluorescence (LIF) spectra of the òB₁(Πu)-X̃²A₁ band system of ¹¹BH₂, ¹⁰BH₂, ¹¹BD₂, and ¹⁰BD₂ have been observed for the first time. The free radicals were "synthesized" by an electric discharge through a precursor mixture of 0.5% diborane (B₂H₆ or B₂D₆) in high pressure argon at the exit of …