Chemistry Commons^™

Characterization Of Ceriporiopsis Subvermispora Bicupin Oxalate Oxidase Expressed In Pichia Pastoris, Patricia Moussatche, Alexander Angerhofer, Witcha Imaram, Eric Hoffer, Kelsey Uberto, Christopher Brooks, Crystal Bruce, Daniel Sledge, Nigel G. J. Richards, Ellen W. Moomaw

Faculty Articles

Oxalate oxidase (E.C. 1.2.3.4) catalyzes the oxygen-dependent oxidation of oxalate to carbon dioxide in a reaction that is coupled with the formation of hydrogen peroxide. Although there is currently no structural information available for oxalate oxidase fromCeriporiopsis subvermispora (CsOxOx), sequence data and homology modeling indicate that it is the first manganese-containing bicupin enzyme identified that catalyzes this reaction. Interestingly, CsOxOx shares greatest sequence homology with bicupin microbial oxalate decarboxylases (OxDC). We show that CsOxOx activity directly correlates with Mn content and other metals do not appear to be able to support catalysis. EPR spectra indicate that the Mn is present …

Assessment Of Conceptual Understanding Of Atomic Structure, Covalent Bonding, And Bond Energy, Alma Gonzales

All Theses

This research work relied upon the importance of conceptual understanding to meaningful learning. Conceptual understanding is strongly influenced by students' prior knowledge (1). Many of these ideas pose strong barriers to deeper understanding and are called misconceptions since they are inconsistent or in conflict with generally accepted scientific facts (2). Thus, it is beneficial for instructors to initially elicit students' conceptual understanding in order to properly address student's misconceptions during the learning process. However, results are very dependent on the instrument used to elicit conceptual understanding (3). The most commonly used tools are summative assessments or achievement tests (4). They …

Computational Study Of Passive Neutron Albedo Reactivity (Pnar) Measurement With Fission Chambers, Sandra De La Cruz

UNLV Theses, Dissertations, Professional Papers, and Capstones

The Passive Neutron Albedo Reactivity technique (PNAR) was used to assay used nuclear fuel as a potential method for the measurement of fissionable material in fuel assemblies. A Monte Carlo transport code (MCNPX 2.6) was used to develop simulation models to evaluate the PNAR technique. The MCNPX simulated models consisted of two 17x17 Pressurized Water Reactor (PWR) used fuel assemblies; one with an initial 3 wt% uranium-235*, cooled for 20 years and second with an initial 4 wt% uranium-235*, cooled for 5 years. Each used fuel assembly was simulated at four different burn up rates of 15, 30, 45, and …

Scope And Mechanistic Studies Of The Palladium On Carbon Catalyzed Suzuki Cross Coupling Reaction, Carl Leblond

Seton Hall University Dissertations and Theses (ETDs)

No abstract provided.

Synthesis, Characterization, And Reactivity Of Biologically Relevant Copper(I) Selone And Thione Complexes, Martin Kimani

All Dissertations

In Fenton-like reactions, Cu+ localized on DNA reduces hydrogen peroxide to form hydroxyl radical (*OH), resulting in oxidative DNA damage. This DNA damage causes mutation and cell death, which can lead to diseases such as cancer, Alzheimer's, and arteriosclerosis. Sulfur and selenium antioxidants have been investigated for the prevention and treatment of these diseases, and studies have shown that sulfur- and selenium-containing antioxidants prevent DNA damage from copper-generated hydroxyl radical and that metal coordination is required for the observed antioxidant activity.
To determine how copper coordination results in DNA damage inhibition, Cu+ complexes with selone and thione ligands were synthesized …

Particle Beam Glow Discharge Spectroscopy As A Tool For Speciation And Metallomics Analysis, Charles Quarles Jr

All Dissertations

Metallomics is a growing field of interdisciplinary research that investigates metals in biological and environmental systems. One of the major problems in detecting metals in biological systems is the instrumentation required to analyze these complex biological samples. Typically, an inductively coupled plasma-optical emission spectrometer or -mass spectrometer (ICP - OES or - MS) is used for elemental analysis and an electrospray ionization-mass spectrometer (ESI-MS) is used for molecular information. In almost all cases, the sample introduction matrix is different for each instrument, which can affect the physiological conditions of the sample and change its properties. Particle beam/hollow cathode-optical emission spectroscopy …

Targeting A-Form Nucleic Acids: A Neomycin Based Approach, Nicholas Shaw

All Dissertations

This manuscript reflects our most recent advancements in the recognition of nucleic acids. Chapter one focuses on previously established methods in nucleic acid recognition. Nucleic acid targeting by small molecules affords a unique way to potentially inhibit biological functions, which is different from targeting enzyme and protein bio-macromolecules. We seek to further develop an aminoglycoside approach to targeting nucleic acids. Since aminoglycosides were first introduced, over 60 years ago, as treatment for tuberculosis, natural product discovery and demands for therapeutically more effective aminoglycosides, with lowered toxicity, have dominated the landscape of aminoglycoside research. More recently, our group has established neomycin …

Synthesis And Characterization Of Extended Solids Containing Nano-Sized Transition Metal Oxide Lattices, Matthew Williams

All Dissertations

In this research, focus has been placed on the study of magnetic anomalies due to geometric frustration of magnetic ions. The goal of the study presented in this dissertation was to synthesize pseudo&ndashlow&ndashdimensional (PLD) compounds, those structures showing zero (dot), one (chain), and two (sheet) dimensional lattices observed in extended (3D) host frameworks with enhanced anisotropic physical properties, in an attempt to elucidate some structure&ndashproperty correlations arising from magnetic spin confinement. The scope of this research involved 1) exploratory synthesis of novel, low&ndashdimensional transition metal oxide lattices, specifically Mn and V, embedded in non&ndashmagnetic oxyanion frameworks, either Ge, P, or …

New Interfacial Nanochemistry On Sensory Bioscaffold-Membranes Of Nanobelts, Feng Chen

Graduate Theses and Dissertations

Nanostructured bioscaffolds and biosensors are evolving as popular and powerful tools in life science and biotechnology, due to the possible control of their surface and structural properties at the nm-scale. Being seldom discussed in literature and long-underexploited in materials and biomedical sciences, development of nanofiber-based sensory bioscaffolds has great promises and grand challenges in finding an ideal platform for low-cost quantifications of biological and chemical species in real-time, label-free, and ultrasensitive fashion. In this study, titanate nanobelts were first of all synthesized, from hydrothermal reactions of a NaOH (or KOH solution) with TiO2 powder, to possess underexploited structure and surface …

Self-Assembling Organic Semiconductors With Tunable Electronic Properties Based On Novel Asymmetric Phenazine And Bisphenazine, Kyoungmi Jang

UNLV Theses, Dissertations, Professional Papers, and Capstones

Current demands in the area of organic semiconductors focus on both electronic and self-assembling properties. Particularly, one-dimensionally grown nanostructures of small organic semiconductors have drawn much attention for nanodevice fabrication. Self-assembly through various intermolecular interactions has been widely used to produce one-dimensionally grown nanostructures which can be induced by various methods such as rapid solution dispersion, a phase transfer method, vapor annealing, crystallization, and organogelation in conjunction with proper molecular design. Controlling the morphology of the nanostructures plays an important role in achieving desirable properties in optoelectronic device applications. While significant advancements have been made in developing molecular architectures for …

Symmetry-Based Techniques For Qualitative Understanding Of Rovibrational Effects In Spherical-Top Molecular Spectra And Dynamics, Justin Chadwick Mitchell

Graduate Theses and Dissertations

Using light to probe the structure of matter is as natural as opening our eyes. Modern physics and chemistry have turned this art into a rich science, measuring the delicate interactions possible at the molecular level.

Perhaps the most commonly used tool in computational spectroscopy is that of matrix diagonalization. While this is invaluable for calculating everything from molecular structure and energy levels to dipole moments and dynamics, the process of numerical diagonalization is an opaque one. This work applies symmetry and semi-classical techniques to elucidate numerical spectral analysis for high-symmetry molecules.

Semi-classical techniques, such as the Potential Energy Surfaces, …

Molecular Recognition Of Amino Acids, Peptides, And Proteins By Cucurbit[N]Uril Receptors, Adam R. Urbach, Vijayakumar Ramalingam

Chemistry Faculty Research

At the forefront of the endeavor to understand and manipulate living systems is the design and study of receptors that bind with high affinity and selectivity to specific amino acids, peptides, and proteins. Cucurbit[n]urils are among the most promising class of synthetic receptors for these targets due to their high affinities and selectivities in aqueous media and to the unique combination of electrostatic and hydrophobic interactions that govern binding. The fundamental supramolecular chemistry in this area has been explored in depth, and novel, useful applications are beginning to emerge.

Ligand And Metal Effects On The Co-Release Reactivity Of Metal Acireductone And Flavonolate Complexes, Katarzyna Grubel

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research reported herein involves synthetic metal complexes of relevance to dioxygenase enzymes (Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD) and quercentinase (2,4-flavonol dioxygenase) that promote oxidative carbon-carbon bond cleavage and CO release. The experiments focus on the elucidation of structure-reactivity relationships and evaluation of the conditions under which CO is generated.

It had been proposed that hydrogen bond donors in the secondary environment of the active site metal center in Ni(II)-ARD influence the coordination of the acireductone substrate on the nickel center. To evaluate this proposal, we investigated the Ni(II) coordination chemistry of an acireductone-type enolate anion using a supporting chelate ligand …

Student-Faculty Research In Organic Chemistry, Timo V. Ovaska

Honors and Awards Speeches and Programs

Timo Ovaska remarks that the clothes we wear, the colors we see, the foods we eat, the fuels that power our cars, the medicines that make us heal and feel better, even the biochemical reactions that happen in our bodies are all manifestations of the importance of organic chemistry in daily life.

He also praises his students who chose to do research, as there is no mandatory research component for the chemistry major at Connecticut College, who have gone on to successful careers. Students chose to get involved not because it was going to be easy, but because they were …

Tranformation Theory, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

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 …

Differentiation Of Bacillus Endospores From Gas Chromatography-Mass Spectrometry Of Biomarkers Produced By Thermochemolysis Methylation, Tai Van Truong

Theses and Dissertations

Methods for fast, simple detection of biomarkers to detect and differentiate closely related Bacillus endospores including Bacillus anthracis (BA), Bacillus thuringiensis (BT), Bacillus atrophaeus (BG), and Bacillus cereus (BC) using thermochemolysis and methylation (TCM), coiled wire filament (CWF), solid phase micro extraction (SPME) and gas chromatography-mass spectrometry (GC-MS) were developed. The main biomarkers detected and used for differentiation include dipicolinic acid methyl ester (DPAME), fatty acid methyl esters (FAMEs), 3-methyl-2-butenoic acid methyl ester (3M2BAME), 2-butenoic acid methyl ester (2BAME), and several methylated sugars. TCM of endospores was performed based on hydrolysis and methylation at elevated temperature after the endospores were …

Converting Cooa From A Carbon Monoxide To An Oxygen-Sensing Heme Protein Transcription Factor: Investigations Into The Structure And Mechanism Of Gas Binding, Amanda Sedoris, Josh Wagoner

Symposium on Research and Creative Expression (SORCE)

CooA is a carbon monoxide-sensing (CO-sensing) heme protein transcription factor that regulates gene activation in several bacteria and, importantly, is a convenient model for studying analogous proteins in the human body. In the present study, the specificity and mechanism of gas-binding of CooA have been investigated by efforts to convert CooA from a CO to an oxygen (O₂) sensor through site directed mutagenesis of residues in the gas binding pocket of the heme group.  The resulting mutated proteins were then isolated and characterized with spectroscopy. The results of this research project will provide further insight into the current …

Water Quality Of Restored Wetlands: A Study Of The Great Marsh Complex In The Indiana Dunes National Lakeshore, Wendy Marth, Diandra Obermeyer, Kandace Spera, Pitchaya Patana-Anake, Adam Conner

Symposium on Research and Creative Expression (SORCE)

Historic wetlands are increasingly being restored for multiple purposes, including improving water quality (WQ). The Great Marsh of the Indiana Dunes National Lakeshore (IDNL) serves as an excellent example of a restored wetland that affects WQ. Fifteen different WQ parameters have been monitored at sites throughout the Great Marsh to assess how the restored wetland is functioning. Data collected thus far indicate WQ in the restored Great Marsh is typical of a northwest Indiana wetland and that the Great Marsh is functioning like a typical wetland in this region. For example, total phosphorus analyses indicate substantial phosphorus uptake by the …

Isolating And Sequencing Genes Coding For Metal-Reducing Enzymes In Shewanella Algae, Bry, Diana Stutzman, Thaomy Nguyen, Emily Brennan

Symposium on Research and Creative Expression (SORCE)

The Natural and Accelerated Bioremediation Research (NABIR) Program focuses on efficiently managing and reducing contamination of soil and groundwater by heavy metals and nuclear materials at Department of Energy (DOE) sites across the United States. In an effort to learn how to use microbes to accomplish this goal, four genes that code for metal-reducing enzymes expressed by the soil bacterium Shewanella algae, strain BrY are being sequenced. Polymerase Chain Reaction (PCR) is used to amplify the genes of interest, and the PCR products are purified by cloning and sent to the University of Chicago for sequencing. So far, partial …

Impacts Of The Species Elaeagnus Umbellate On The Soil And Water Quality Of The Pierce Cedar Creek Institute Ecosystem, Yacoub Aljobeh, Kristin Engerer

Symposium on Research and Creative Expression (SORCE)

The species Elaeagnus umbellate, more commonly known as autumn olive, is a shrub that is invasive to the United States and indigenous to East Asia. Even though the autumn olive is not native to North America, it was able to thrive and adapt to the new environment by using its ability to fix nitrogen. Nitrogen-fixing is a process where plants intake molecular nitrogen from the atmosphere and convert it into other forms of nitrogen that can be used by the plants. One of the nitrogen-fixing by-products is nitrate. Excessive amounts of nitrate can easily leach from the plant’s root …

Testing The Potential Of Using Fungi To Convert Human Waste Into Protein, Alex Zapata, Elizabeth Phillippi, Blair Mitchell, Jon Schoer, Michael Watters

Symposium on Research and Creative Expression (SORCE)

We report on the results of a pilot experiment designed to test the potential of filamentous fungi (mold) to reduce solid waste (feces) while converting it into a consumable, high protein food product. Feces represent an untapped resource. Filamentous fungi are natural decomposers with the ability to use this resource. Many filamentous fungi are safe to eat. We examined growth in order to determine the conditions which maximized the rate of conversion of solid waste into fungal biomass. For this pilot, we compared the effect of different lengths of incubation, different methods of aeration, and different available surface area. The …

Epistatic Roles For Pseudomonas Aeruginosa Muts And Dinb (Dna Pol Iv) In Coping With Reactive Oxygen Species-Induced Dna Damage, Laurie H. Sanders, Babho Devadoss, Geraldine V. Raja, Jaime O'Connor, Shengchang Su, Daniel J. Wozniak, Daniel J. Hassett, Anthony J. Berdis, Mark D. Sutton

Chemistry Faculty Publications

Pseudomonas aeruginosa is especially adept at colonizing the airways of individuals afflicted with the autosomal recessive disease cystic fibrosis (CF). CF patients suffer from chronic airway inflammation, which contributes to lung deterioration. Once established in the airways, P. aeruginosa continuously adapts to the changing environment, in part through acquisition of beneficial mutations via a process termed pathoadaptation. MutS and DinB are proposed to play opposing roles in P. aeruginosa pathoadaptation: MutS acts in replication-coupled mismatch repair, which acts to limit spontaneous mutations; in contrast, DinB (DNA polymerase IV) catalyzes error-prone bypass of DNA lesions, contributing to mutations. As part of …

Structure Studies On Lanthanide Technetium Pyrochlores As Prospective Host Phases To Immobilize 99- Technetium And Fission Lanthanides From Effluents Of Reprocessed Used Nuclear Fuels, Thomas Hartmann, Ariana Alaniz

Festival of Communities: UG Symposium (Posters)

We performed a systematic investigation of the incorporation of 99Tc into pyrochlore oxide structures, Ln2Tc2O7, where Ln represents trivalent lanthanide Ln3+ cations, while 99Tc is atetravalent, Tc4+, metal cation. Pyrochlore compounds are high-melting temperature oxides and are recognized for their durability. Our goal in this preliminary study is to characterize and quantify the range of stability of the lanthanum technetium pyrochlore oxide phase. Hereby, powder X-ray diffraction (XRD) and Rietveld analysis were used to determine and characterize the crystalline phase content with high accuracy, and scanning electron microscopy (SEM) was used to characterize the microstructure and homogeneity of the synthesized …

Sustainable Alternative To Non-Biological Nitrogen Fixation To Nitrate For Fertilizers, Patrick Freeze, Glenn Miller

Festival of Communities: UG Symposium (Posters)

Currently, the industrial method of nitrogen fixation for use in fertilizers (Haber- Bosch process [N2 (g) + 3 H2 (g) <--> 2 NH3 (g)]) is our main source of non-biological conversion of atmospheric nitrogen to ammonia. The proposed research experiment utilizes the catalytic mechanism of titanium dioxide which, in the presence of heat or sunlight, undergoes fixation of atmospheric nitrogen. This method of nitrate production could serve as a sustainable source of nitrogen for fertilizers. Variables in the experiment included the manipulation of thermal pressure, heat, and base addition to counteract hydrochloric acid production, a selflimiting byproduct.

Energy Densification Via Hydrothermal Carbonization, Keri Noack

Festival of Communities: UG Symposium (Posters)

A process called hydrothermal carbonization (HTC), also known as wet torrefaction involves treatment of raw biomass in hot, pressurized water. HTC of woody biomass has been shown to significantly increase the energy density of the feedstock, producing a biochar, similar to coal, having up to 40% higher calorific energy content. Feedstocks investigated include Tahoe chips, Pinion/Juniper chips, Rice hulls, and Corn Stover pellets pre-treated at 215 °C, 255 °C, and 295 °C. Chemical analyses were conducted on the gaseous, aqueous, and solid HTC products. Energy contents of the solid biochar products were measured by calorimetry, and mass balances were determined.

Predicting Homo And Lumo Energy Gaps For Organic Semi-Conductor: A Theoretical Study, Padtaya Pukpayat

Festival of Communities: UG Symposium (Posters)

This poster presents a theoretical approach for characterizing the electronic properties of novel electron-deficient organic semiconductors containing variety of electron donor substituents. In treating these compounds, the following questions will be addressed: What effects to the bandgap will each substituent have? Will any of the substituents lower the band gap to the desired range for solar cell applications(<2.0eV)? Can we use the current, inexpensive and tractable computational methods as a predictive tool for guiding future experimental design of organic based solar cells, rather than depending solely on experimental procedures?

Luminescent Ionic Liquid Crystals Based On Stilbazolium Moieties, William Mccurdy, Pradip K. Bhowmik

Festival of Communities: UG Symposium (Posters)

Liquid crystals have become pivotally important to a variety of image displaying technologies. They have drawn much attention due to their ability to confer luminescent properties to a wide spectrum of image based devices. The purpose of this research is to describe a new methodology for an efficient synthesis of luminescent ionic liquid crystals including a discussion of their applications in the biological/medicinal sciences.

Characterization Of Ips Pini Ipsdienol Dehydrogenase (Idol Dh), Heidi Pak, Claus Tittiger, William Welch

Festival of Communities: UG Symposium (Posters)

Ipsdienol is an important pheromone component for pine engraver beetle, Ips pini. Ipsdienol is a ten carbon monoterpenoid secondary alcohol and ipsdienone is the corresponding ketone. We are characterizing the activity of recombinant IDOL DH produced in Sf9 (insect) cells. The enzyme has a high stereospecificity: (-) ipsdienol was found to be a substrate while (+)-ipsdienol was neither a substrate nor inhibitor. Closely related monoterpenoids, such as nerol, geraniol, and citral, were neither substrates nor inhibitors. Smaller compounds, such as 2-propanol, also failed to act as an inhibitor or substrate. This indicates the binding site of this enzyme is highly …

Dicarbonyldichloridobis(Trimethylphosphane)Iron(Ii)–Carbonyldichloridotris(Trimethylphosphane)Iron(Ii)–Tetrahydrofuran (1/1/2), Nigam Rath, Meghan Stouffer, Matthew Janssen, John Bleeke

Chemistry & Biochemistry Faculty Works

The asymmetric unit of the title crystal, [FeCl2(C3H9P)3(CO)]·[FeCl2(C3H9P)2(CO)2]·2C4H8O, contains half mol­ecules of the two closely related FeII complexes lying on mirror planes and a tetra­hydro­furan solvent mol­ecule, one C atom of which is disordered over two sets of sites with site occupancy factors 0.633 (9) and 0.367 (9). In both FeII complex mol­ecules, a distorted octa­hedral coordination geometry has been observed around the Fe atoms. Weak intermolecular C-H...O inter­actions are observed in the crystal structure.