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Adsorbents With Chemically Bonded Saccharide Surfaces: Synthesis And Application For Stereoisomer Separation And The Synthesis Of Chiral Porous Silicas Using Templates Chiral Surfactant, Edwin Vega

Seton Hall University Dissertations and Theses (ETDs)

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Probing Ground-State Single-Electron Self-Exchange Across A Molecule−Metal Interface, Yuanmin Wang, Papatya C. Sevinc, Yufan He, H. Peter Lu

Chemistry Faculty Publications

We have probed single-molecule redox reaction dynamics of hemin (chloride) adsorbed on Ag nanoparticle surfaces by single-molecule surface-enhanced Raman spectroscopy (SMSERS) combined with spectroelectrochemistry. Redox reaction at the molecule/Ag interface is identified and probed by the prominent fluctuations of the Raman frequency of a specific vibrational mode, nu(4), which is a typical marker of the redox state of the iron center in a hemin molecule. On the basis of the autocorrelation and cross-correlation analysis of the single-molecule Raman spectral trajectories and the control measurements of single-molecule spectroelectochemistry and electrochemical STM, we suggest that the single-molecule redox reaction dynamics at the …

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 …

Protein-Lipid Interactions: Influence Of Anchoring Groups And Buried Arginine On The Properties Of Membrane-Spanning Peptides, Vitaly V. Vostrikov

Graduate Theses and Dissertations

Designed transmembrane peptides were employed for investigations of protein-lipid interactions by means of oriented solid-state deuterium NMR spectroscopy using isotope-enriched alanine residues. Using the model GWALP23 sequence (GGALW(LA)6LWLAGA) as a host peptide having single interfacial tryptophan anchor residues, the effects of different guest mutations were explored. Replacements of glycine residues 2 and 22 to positively charged lysine or arginine on both termini had little influence on the peptide average orientation. Conversely, glycine to tryptophan substitutions had profound effects, manifested in the increased dynamics and altered tilt direction of the peptide. While the charged residues at the peptide termini did not …

Mechanisms Of Non-Enzymatic Peptide Bond Formation: Thioester And Transamidation Routes, Danielle Amie Landry

Master's Theses

The reaction mechanisms employed during non-ribosomal peptide (amide) synthesis in the non-ribosomal modular enzyme complex and in the enzyme glutaminyl cyclase were also used for spontaneous peptide (amide) synthesis in a buffered, abiotic solution. Analytical analyses revealed that spontaneous peptide (amide) bond formation occurred under mild prebiotic conditions during both the thioester-based production of phenylalanine peptides and peptidyl thioesters, and the spontaneous cyclization of glutamine t-butyl ester (Gln-tbe) into pyroglutamic acid t-butyl ester. Internal standard-based quantitative MS determined that 4.9 x 10-5 sec-1 was the rate constant for spontaneous Gln-tbe cyclization in imidazole buffer, pH 7, at 50°C, and that …

Synthetic Dosage Lethality Screen With Actin Cytoskeleton In Yeast, Jessica Cho

Renée Crown University Honors Thesis Projects - All

The actin cytoskeleton is a vitally important organizing structure found in the cytoplasm of our cells. It contributes to essential cell functions from growth and cell division, development, signal transduction, adaptation, to gene expression. Interest in how regulation of the actin cytoskeleton---due to actin cytoskeleton's importance to cell function-may contribute to diverse human disease states such as the rampant cell division and metastasis that occurs in cancerous tissues. It has been further elucidated that many human genetic disorders are the result of complex haploinsufficiencies (CHI) and/or altered gene dosages at multiple loci. By reviewing a large number of potential Synthetic …

Quantum Dot Biofunctionalization, Nathaniel J. Miska

Renée Crown University Honors Thesis Projects - All

We have shown the efficacy of Quantum Dots (qdots), nano-scale fluorescent particles made of semi-conductive material, as versatile biologically functional research tools. This functionality depends upon a series of chemical transformations that produce stable, aqueous, biomolecule-bound qdots with high quantum yield. We utilize the metal binding and chelating properties of the amino acid histidine to displace hydrophobic surface ligands and to phase-transfer qdots from organic to aqueous media. The intermediate binding strength of histidine to qdot surface facilitates its exchange with a variety of strongly binding thiolated biomolecules. Ligand profiles are subsequently characterized via FTIR, NMR, and gel electrophoresis. Negatively-charged …

Bismuth Nitrate-Induced Novel Nitration Of Eugenol And Estradiol: An Exploratory Study, Luis Canales

Theses and Dissertations - UTB/UTPA

Molecules originating in nature have held an important place in chemistry and in society. Many of the important useful compounds of all time were first discovered in nature. Eugenol, a multi-functionalized biologically active constituent, is present in high quantity in natural clove. Eugenol is an important herb due to its medicinal activities; therefore, research on this molecule is necessary. Nitration of Eugenol was performed through various metal nitrates and solid surface combinations. Estrogens are contributors of the development of many secondary sex characteristics in females; they play various important roles in the nervous system. Direct nitration of estradiol has been …

Biocompatibility Of Electrospun Polymer Nanofibers (Epns) With Nih 3t3 Cell Line And Interaction Of Quercetin With Different Flavonoids: Induction Of Phase Ii Enzymes In Vitro Cancer Cell Lines, Brenda S. Benavides

Theses and Dissertations - UTB/UTPA

Part I: In this study Electrospun nanofibers, Elasthane™ 55D, Elasthane™ 75D, Biospan®, Hydrothane™ and Lycra® were evaluated for their biocompatibility to be artificial tissue substitutes using NIH-3T3 fibroblast cells. A colorimetric based MTT dye reduction assay demonstrated that EPNs did not stop cell growth in vitro. Additionally, fluorescence confocal microscope images verified that cell adhesion occurred in the nanofibers, and cell growth on the EPNs over two weeks period was confirmed by DNA quantification.

Part II: This section of the thesis is focused on evaluation of chemopreventive properties of various phytochemicals by induction of Phase II enzymes. The interaction of …

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 …

Oxidative Derivatization Of Folic Acid Monitored By Capillary Electrophoresis With Uv Absorbance And Fluorescence Detection, Jeffrey P. Cunniff

Honors Capstones

No abstract provided.

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 …

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.

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 …

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 …

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 …

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, …

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 …

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 …

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 …

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.

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.

Trypanosoma Cruzi - Derived Sugar Epitopes - Synthesis And Immunology, Erika Y. Monroy^, Roger A. Ashmus, Jamal Khamsi, Andrew Pardo, Nathaniel S. Schocker, Rosa A. Maldonado, Kayla Vasquez, Alexandre F. Marques, Igor C. Almeida, Katja Michael*

COURI Symposium Abstracts, Spring 2011

The protozoan parasite Trypanosoma cruzi is the causative agent of Chagas disease. As of today no effective vaccine has been developed for it. Certain developmental stages of T.cruzi express cell surface oligosaccharides with terminal alpha-galactosyl and rhamnosyl residues, which are believed to be highly immunogenic in humans. The exact structures and sizes of these epitopes are still unknown. Our quest is to shine light on the chemical structures of immunogenic alpha-Gal and alpha-Rha containing mono-, di-, and trisaccharides that are conjugated to a keyhole limpet hemocyanin (KLH) carrier protein through a combination of chemical synthesis and immunological studies. The compounds …