Chemistry Commons^™

Antimicrobial Properties Of Isomers Of Benzofuranylethanol, Nick Cheatwood, Jessica Bronstad, Michele Harris

Undergraduate Research Conference

A biotransformaDon reacDon is a chemical conversion of a substance into a desired product with the aid of whole, living cells containing the necessary enzymes. In addiDons to living cells, other substances, such as vegetable strips, will also catalyze biotransformaDon reacDons. Advantages of biotransformaDon reacDons include the following: the ability to recycle material, the use of less hazardous chemicals, the ability to compost vegetable strips, the use of inexpensive materials that are locally available, and the ability to produce a single isomer. The biotransformaDon reacDon for the conversion of benzofuranyl methyl ketone (BMK) to (-)-benzofuranylethanol (BMA) using carrot strips as …

Electronic Cigarettes: Truth Or Toxic?, Timothy S. Turner, Alyx S. Frantzen

Undergraduate Research Conference

With the increasing research on the hazards of cigareDes, people are looking for a safer alterna>ve to smoking. Electronic CigareDes were introduced in the early 2000’s to serve this purpose, and they are gaining increasing popularity. Many e-cigareDe companies claim that the use of e-cigareDes is completely harmless because of combus>on of the organic liquids would cause the inhala>on of only water vapor and carbon dioxide along with the flavors and nico>ne. Companies also adver>se their products to help smokers quit smoking. Recently, “vaping” has grown increasingly popular especially with minors since several states s …

Characteristic Length Scales Of The Secondary Relaxations In Glass-Forming Glycerol, Sudipta Gupta, Eugene Mamontov, Niina Jalarvo, Laura Stingaciu, Michael Ohl

Faculty Publications

We investigate the secondary relaxations and their link to the main structural relaxation in glass-forming liquids using glycerol as a model system. We analyze the incoherent neutron scattering signal dependence on the scattering momentum transfer, Q , in order to obtain the characteristic length scale for different secondary relaxations. Such a capability of neutron scattering makes it somewhat unique and highly complementary to the traditional techniques of glass physics, such as light scattering and broadband dielectric spectroscopy, which provide information on the time scale, but not the length scales, of relaxation processes. The choice of suitable neutron scattering techniques depends …

Tool Trouble: Challenges With Using Self-Report Data To Evaluate Long-Term Chemistry Teacher Professional Development, Deborah Herrington, Ellen J. Yezierski, Senetta F. Bancroft

Peer Reviewed Articles

The purpose of this study was to compare the ability of different instruments, independently developed and traditionally used for measuring science teachers’ beliefs in short-term interventions, to longitudinally measure teachers’ changing beliefs. We compared the ability of three self-report instruments (Science Teaching Efficacy Belief Instrument Form A [STEBI], Teaching of Science as Inquiry instrument [TSI], Inquiry Teaching Beliefs instrument [ITB]) and one observational instrument (Reformed Teaching Observation Protocol [RTOP]) to appropriately measure high school chemistry teachers’ beliefs as they engaged in a two and a half year professional development program. Collectively our findings from these four instruments, across three separate …

Synthesis, Isolation, And Characterization Of Potentially Carcinogenic Arginine-Based Heterocyclic Amines, Zachary Reichert

Honors Theses

Previous research demonstrates that meat cooked at high temperatures produces heterocyclic amines (HCAs)—a class of carcinogenic molecules—from burned creatin(in)e and amino acids. However, research performed in our lab, as well as in the peer-reviewed literature, suggests that substituting arginine for creatin(in)e may lead to HCA formation. Arginine is structurally similar to creatin(in)e and can be found abundantly in soy-based food products. Therefore, we have burned arginine and phenylalanine to investigate the potential formation of arginine-based HCAs. The present study attempts to isolate and characterize these potential arginine-HCAs.

Synthesis And Evaluation Of Symmetrical Biphenyltetrols As Aggregation Inhibitors For Alzheimer’S Amyloid-Β Peptide, Sarah L. Wicks, James M. Hanna, Robin Lammi

The Winthrop McNair Research Bulletin

Inhibiting the aggregation of amyloid-beta peptide (Aβ) is one therapeutic target for the prevention and treatment of Alzheimer’s disease. We have previously demonstrated that biphenyl-3,3′,4,4′-tetrol (3,4-BPT) effectively abrogates Aβ aggregation at stoichiometric concentrations. To investigate molecular architecture and determine how the positioning of the hydroxyl hydrogen-bond donors impacts inhibitor efficacy, we have synthesized four additional symmetrical biphenyltetrols (2,3-, 2,4- 2,5- and 3,5-BPT). We have evaluated these inhibitors by means of Congo red and Thioflavin T dye-binding assays to monitor Aβ aggregation as a function of time and to determine inhibitor IC50 values for reducing equilibrium levels of aggregation. 2,3- and …

Purification And Characterization Of Nickel Uptake Regulator (Nur) And Single Nur Mutants From Streptomyces Coelicolor, Denise Peppers, Nick Grossoehme

The Winthrop McNair Research Bulletin

The Nickel Uptake Regulator (NUR) is a metalloregulatory protein found in the microorganism Streptomyces coelicolor. S.coelicolor is a gram-positive bacterium that plays an important role in antibiotic production. NUR is responsible for the uptake of nickel and the regulation of the enzyme Superoxide Dismutase (SOD) within S.coelicolor. NUR regulates Fe-and Ni-SODs through direct and indirect transcription processes, respectively. The goal of this research is to purify and characterize the metal and DNA binding affinities in Wild Type (WT) NUR. There are two metal binding sites within NUR that is believed to contribute to the function of this protein. These sites …

The Reaction Of O-Silylated Cyanohydrin Anions With Epoxides As An Alternative For The Enantio- And Diastereoselective Preparation Of Aldols, Diamond Rose Melendez, Aaron Hartel

The Winthrop McNair Research Bulletin

The aldol addition is one of the most important and most utilized carbon-carbon bond forming reactions in chemical synthesis. This reaction, between an aldehyde or ketone and a second, enolized aldehyde or ketone, results in the formation of a -hydroxycarbonyl (often referred to as an “aldol product” or “aldol”). Modern variations of the aldol reaction have allowed for enantio- and diastereoselectivity in the reaction; however, many of these methods have undesirable drawbacks such as the use of expensive chiral auxiliaries. The chiral auxiliaries require additional synthesis steps for their introduction and removal and cannot be completely recovered after the reaction …

Cloning And Characterization Of Nickel Uptake Regulator Nur Mutants From Streptomyces Coelicolor, Olivia Manley, Nick E. Grossoehme

The Winthrop McNair Research Bulletin

Sufficient concentrations of metal within a cell are required for proper cellular function; however, metals become toxic at very high concentrations. Therefore, it is important for an organism to have a mechanism for maintaining metal homeostasis within its cells. Streptomyces coelicolor, a soil-dwelling bacterium important in the production of antibiotics, utilizes the nickel uptake regulator (NUR) to maintain nickel homeostasis and oxidative response. NUR functions as a transcriptional repressor that responds to changing cytosolic concentrations of Ni²⁺. Previous research describes two key metal-binding sites per NUR monomer. Our research seeks to analyze how changes to these binding …

Metabolomics Reveals New Mechanisms For Pathogenesis In Barth Syndrome And Introduces Novel Roles For Cardiolipin In Cellular Function, Yana Sandlers, Kelly Mercier, Wimal Pathmasiri, Jim Carlson, Susan Mcritchie, Susan Sumner, Hilary J. Vernon

Chemistry Faculty Publications

Barth Syndrome is the only known Mendelian disorder of cardiolipin remodeling, with characteristic clinical features of cardiomyopathy, skeletal myopathy, and neutropenia. While the primary biochemical defects of reduced mature cardiolipin and increased monolysocardiolipin are well-described, much of the downstream biochemical dysregulation has not been uncovered, and biomarkers are limited. In order to further expand upon the knowledge of the biochemical abnormalities in Barth Syndrome, we analyzed metabolite profiles in plasma from a cohort of individuals with Barth Syndrome compared to age-matched controls via ¹H nuclear magnetic resonance spectroscopy and liquid chromatography-mass spectrometry. A clear distinction between metabolite profiles of …

Glycine N-Acyltransferase-Like 3 Is Responsible For Long-Chain N-Acylglycine Formation In N18Tg2 Cells, Kristen A Jeffries, Daniel R Dempsey, Emma K Farrell, Ryan L Anderson, Gabrielle J Garbade, Tatyana S Gurina, Imran Gruhonjic, Carly A Gunderson, David J Merkler

Chemistry Faculty Publications

Long-chain fatty acid amides are signaling lipids found in mammals and other organisms; however, details of the metabolic pathways for the N-acylglycines and primary fatty acid amides (PFAMs) have remained elusive. Heavy-labeled precursor and subtraction lipidomic experiments in mouse neuroblastoma N18TG2 cells, a model cell line for the study of fatty acid amide metabolism, establish the biosynthetic pathways for the N-acylglycines and the PFAMs. We provide evidence that the N-acylglycines are formed by a long-chain specific glycine-conjugating enzyme, glycine N-acyltransferase-like 3 (GLYATL3). siRNA knockdown of GLYATL3 in the N18TG2 cells resulted in a decrease in the levels of the N-acylglycines …

Optimizing Protocols For Carbohydrate Nmr Chemical Shift Computations, Michael Trent Kemp

USF Tampa Graduate Theses and Dissertations

The spectroscopic analysis of cellulose is experimentally challenging while computationally accessible with recent developments in NMR code. However, prior to using density functional theory to calculate the NMR chemical shifts of cellulose, smaller, sugar-like molecule systems need to be benchmarked against experimental values. The quantum mechanical / molecular mechanical (QM/MM) calculations presented herein utilize six test systems: ethanol, pyridine, pyrrolidine, pyrrole, myo-inositol and scyllo-inositol in conjunction with the reference tetramethylsilane used to scale the calculated isotropic shielding tensors to relative chemical shifts. The effect of solvent on calculated NMR chemical shifts has also been investigated with regard to quantity of …

Removal Of Perfluorooctanoic Acid From Water Using Primitive, Conventional And Novel Carbonaceous Sorbent Materials, Christopher K. Brown

Theses and Dissertations

Polyfluoroalkyl Substances (PFAS), like perfluorooctanoic acid, have been used for the last 50 years in a wide variety of industrial processes and consumer-based products, including polymer additives, lubricants, fire retardants and suppressants, pesticides, and surfactants (Buck et al. 2015). The Department of Defense (DoD) has used PFAS-based Aqueous Film Forming Foam (AFFF) at fire training facilities and aircraft hangars. AFFF has contaminated approximately 600 sites classified as fire training facilities with PFAS (Huang, 2013).

This study focused on testing the most likely carbonaceous adsorbent compounds to remediate PFAS-contaminated sites on Air Force installations. Batch tests were performed to determine the …

Light-Activated Compounds, Edith C. Glazer, David K. Heidary

Chemistry Faculty Patents

The presently-disclosed subject matter includes light-activated ruthenium compounds. In some embodiments the compounds release one or more ligands when exposed to light, and in specific embodiments the light includes a wavelength of about 500 nm to about 1000 nm. The present compounds can also comprise an overall charge, wherein the overall charge can be a positive overall charge or a negative overall charge. Further still, embodiments include methods of treating cancer in a subject by administering a compound and then exposing a site of the subject to light.

Glass Polymorphism In Glycerol–Water Mixtures: Ii. Experimental Studies, Johannes Bachler, Violeta Fuentes-Landete, David A. Jahn, Jessina Wong, Nicolas Giovambattista, Thomas Loerting

Publications and Research

We report a detailed experimental study of (i) pressure-induced transformations in glycerol–water mixtures at T = 77 K and P = 0–1.8 GPa, and (ii) heating-induced transformations of glycerol–water mixtures recovered at 1 atm and T = 77 K. Our samples are prepared by cooling the solutions at ambient pressure at various cooling rates (100 K s1–10 K h1) and for the whole range of glycerol mole fractions, wg. Depending on concentration and cooling rates, cooling leads to samples containing amorphous ice (wg Z 0.20), ice (wg r 0.32), and/or ‘‘distorted ice’’ (0 o wg r 0.38). Upon compression, we …

The Biomolecule Sequencer Project: Nanopore Sequencing As A Dual-Use Technology For Crew Health And Astrobiology Investigations, K. K. John, D. S. Botkin, A. S. Burton, S. L. Castro-Wallace, J. D. Chaput, J. P. Dworkin, Niles Lehman, M. L. Lupisella, C. E. Mason, D. J. Smith, S. Stahl, C. Switzer

Chemistry Faculty Publications and Presentations

Human missions to Mars will fundamentally transform how the planet is explored, enabling new scientific discoveries through more sophisticated sample acquisition and processing than can currently be implemented in robotic exploration. The presence of humans also poses new challenges, including ensuring astronaut safety and health and monitoring contamination. Because the capability to transfer materials to Earth will be extremely limited, there is a strong need for in situ diagnostic capabilities. Nucleotide sequencing is a particularly powerful tool because it can be used to: (1) mitigate microbial risks to crew by allowing identification of microbes in water, in air, and on …

Chemical Reaction Kinetics Of The Pictet-Spengler Reaction, Jo Ann K. Girel

College of Science and Health Theses and Dissertations

There is an extensive history of the use of alkaloids for medicinal purposes. Today, development of novel pharmaceutical alkaloids is imperative to developing effective drugs. The Pictet-Spengler reaction of dopamine with 4-hydroxyphenyl-acetaldehyde is the first step in the biosynthesis of thousands of known alkaloids. In this reaction, mechanisms have been proposed to explain the specificity of phosphate catalysis. However, the uniqueness of the phosphate ion in the Pictet-Spengler reaction is not explained. The Pictet-Spengler reaction of dopamine with propanal in phosphate buffer and in maleic acid buffer were evaluated and determined to be comparable. The reaction was found to be …

A Systematic Investigation Of Structure/Function Requirements For The Apolipoprotein A-I/Lecithin Cholesterol Acyltransferase Interaction Loop Of High-Density Lipoprotein, Xiaodong Gu, Zhiping Wu, Ying Huang, Matthew A. Wagner, Camelia Baleanu Gogonea, Ryan A. Mehl, Jennifer A. Buffa, Anthony J. Didonato, Leah B. Hazen, Paul L. Fox, Valentin Gogonea, John S. Parks, Joseph A. Didonato, Stanley L. Hazen

Chemistry Faculty Publications

The interaction of lecithin-cholesterol acyltransferase (LCAT) with apolipoprotein A-I (apoA-I) plays a critical role in high-density lipoprotein (HDL) maturation. We previously identified a highly solvent-exposed apoA-I loop domain (Leu159–Leu170) in nascent HDL, the so-called “solar flare” (SF) region, and proposed that it serves as an LCAT docking site (Wu, Z., Wagner, M. A., Zheng, L., Parks, J. S., Shy, J. M., 3rd, Smith, J. D., Gogonea, V., and Hazen, S. L. (2007) Nat. Struct. Mol. Biol. 14, 861–868). The stability and role of the SF domain of apoA-I in supporting HDL binding and activation of LCAT are debated. Here we …

Modified Yttrium Hydroxide/Mc Nylon Nanocomposites And Scaling Effects In Multilayer Polyethylene Films, Jia Chen

USF Tampa Graduate Theses and Dissertations

In this thesis, monomer casting (MC) nylon was synthesized. MC nylon could replace nonferrous metals in certain applications, including gears, wheels, and other moving parts. However, compared with metals, MC nylon products have poor strength and stiffness, and crack easily, especially at low temperatures. In addition, the dimensional stability of MC nylon is poor, especially in the large casting nylon products, causing significant internal stresses due to shrinkage. Thus, MC nylon cracks easily when cast and molded. The yttrium hydroxide particles were modified by stearic acid and dispersed in the caprolactam. The polymerization time was short due to fast anionic …

Αβ-Peptide Mimics Of Z-Domain Peptides, Samuel H. Gellman, James W. Checco

Department of Chemistry: Faculty Publications

Described are αβ-peptide mimics of Z-domain scaffold pep tides, methods of making them, and methods of using them. The αβ-peptide mimics include B-amino acid residues and, optionally, disulfide bonds to stabilize the conformation of the mimics. The compounds may be truncated as compared to conventional Z-domain scaffold peptides and are resistant to proteolytic degradation due to the presence off-amino acid residues. The mimics can be made so as to bind selectively to a desired target.

Hydrogen Bonded And Stacked Geometries Of The Temozolomide Dimer, Okuma Emile Kasende, Jules Tshishimbi Muya, Vincent De Paul Nzuwah-Nziko, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Dispersion-corrected Density Functional Theory (DFT) and MP2 quantum chemical methods are used to examine homodimers of temozolomide (TMZ). Of the twelve dimer configurations found to be minima, the antarafacial stacked dimer is the most favored, lower in energy than coplanar dimers which are stabilized by H-bonds. The comparison between B3LYP and B3LYP-D binding energies points to dispersion as a primary factor in stabilizing the stacked geometries. CO(π)→CO(π*)charge transfers between amide groups in the global minimum are identified by NBO, as well as a pair of weak CH∙∙N H-bonds. AIM analysis of the electron density provides an alternative description which includes …

Poly(Ester Amide)S With Pendant Azobenzenes: Multi-Responsive Self-Immolative Moieties For Modulating Polymer Assemblies, Andrew D. Wong, Alex Prinzen, Elizabeth Gillies

Chemistry Publications

Azobenzenes are well-known for their trans–cis photoisomerization, but it was recently demonstrated that azobenzene derivatives could also undergo reduction to trigger a 1,6-elimination and initiate de- polymerization of a self-immolative polymer. Herein we explore the optimization of azobenzenes as reduction-sensitive moieties, and their incorporation into functional materials. A library of azobenzenes with electron-withdrawing groups was synthesized, and their rates of reduction by hydrazine were deter- mined. Unexpectedly, a 2-Cl substituent increased the rate of reduction more than other electronegative or sterically-demanding substituents. Next, a new diester monomer containing the 2-Cl-azobenzene was synthesized and incorporated into a poly(ester amide) (PEA) backbone, …

An Effective Method For The Preparation Of High Temperature Stable Anatase Tio2 Photocatalysts, Rachel Fagan, Declan Mccormack, Suresh Pillai, Damian Synnott

Articles

An efficient, rapid and straightforward method for the preparation of nitrogen and fluorine (N, F) codoped high temperature stable anatase using a microwave pre-treatment is reported. Using a single source, ammonium fluoride (NH₄F) for both nitrogen and fluorine, effective doping of the precursor titanium isopropoxide (TTIP) was possible. These samples were characterised for their structural and optical properties using X-ray diffraction (XRD), Fourier transform IR (FTIR), Raman spectroscopy and UV-vis spectroscopy. In terms of the anatase to rutile transition enhancement using a novel microwave assisted technique, the sample prepared in a composition of 1:8 TiO₂: NH …

Literature-Based Problems For Introductory Organic Chemistry Quizzes And Exams, Kevin M. Shea, David J. Gorin, Maren E. Buck

Chemistry: Faculty Publications

Literature-based problems expose students to current, real world applications of chemistry. These types of problems are often confined to graduate and advanced undergraduate courses. We describe incorporation of literature-based problems in Organic I and II courses on quizzes and exams. We give students at least 1 week to study and discuss portions of a paper, then ask students to answer quiz and exam questions based on the paper. Students show high levels of engagement with and interest in the primary chemical literature when faced with these types of assessments.

Novel Biodegradable Protonic Ionic Liquid For The Fischer Indole Synthesis Reaction, William C. Neuhaus, Ian J. Bakanas, Joseph R. Lizza, Charles T. Boon Jr., Gustavo Moura-Letts

College of Science & Mathematics Departmental Research

Novel eco-friendly tetramethylguanidinium propanesulfonic acid trifluoromethylacetate ([TMGHPS][TFA]) ionic liquid was developed as catalyst and medium for the Fischer indole synthesis of a wide variety of hydrazines and ketones. The indole products were isolated in high yields and with minimal amounts of organic solvent. This reaction showed that [TMGHPS][TFA] can be regenerated and reused with reproducible yields without eroding the integrity of the ionic liquid.

“Zipped Synthesis” By Cross-Metathesis Provides A Cystathionine Β‑Synthase Inhibitor That Attenuates Cellular H2S Levels And Reduces Neuronal Infarction In A Rat Ischemic Stroke Model, Christopher D. Mccune, Su Jing Chan, Matthew L. Beio, Weijun Shen, Woo Jin Chung, Laura M. Szczesniak, Chou Chai, Shu Qing Koh, Peter T.-H. Wong, David B. Berkowitz

David Berkowitz Publications

The gaseous neuromodulator H₂S is associated with neuronal cell death pursuant to cerebral ischemia. As cystathionine β-synthase (CBS) is the primary mediator of H2S biogenesis in the brain, it has emerged as a potential target for the treatment of stroke. Herein, a “zipped” approach by alkene cross-metathesis into CBS inhibitor candidate synthesis is demonstrated. The inhibitors are modeled after the pseudo-C₂-symmetric CBS product (L,L)-cystathionine. The “zipped” concept means only half of the inhibitor needs be constructed; the two halves are then fused by olefin cross-metathesis. Inhibitor design is also mechanism-based, exploiting the favorable kinetics associated with …

Theoretical Investigation Of Interaction Between The Set Of Ligands And Α7 Nicotinic Acetylcholine Receptor, O. E. Glukhova, Tatiana Prytkova, D. S. Shmygin

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Nicotinic acetylcholine receptors (nAChRs) are neuron receptor proteins that provide a transmission of nerve impulse through the synapses. They are composed of a pentametric assembly of five homologous subunits (5 α7 subunits for α7nAChR, for example), oriented around the central pore. These receptors might be found in the chemical synapses of central and peripheral nervous system, and also in the neuromuscular synapses. Transmembrane domain of the one of such receptors constitutes ion channel. The conductive properties of ion channel strongly depend on the receptor conformation changes in the response of binding with some molecule, f.e. acetylcholine. Investigation of interaction between …

Session F-2: Simple Chemistry Labs And Activities To Teach Difficult And Important Concepts, Dave Devol, Deb Scarano, Anita White

Professional Learning Day

This will be a hands-on session where participants will perform four chemistry activities/experiments (two of the experiments will be a variation on one theme). The topics will include bonding, equilibrium, and stoichiometry. Teachers will be provided with copies of the activities to take back to their classes. In the spirit of learning together, we ask participants to bring their favorite activity/lab to share with the group (these labs will not be performed, just shared. Bringing an activity to share is optional, not required).

Nanomaterials Used To Destroy Water Contaminants, Roger Harrison

Journal of Undergraduate Research

1. Evaluation of how well the academic objectives of the proposal were met

Students working in the mentoring environment synthesized nanomaterials composed of ZnO and characterized the materials by SEM, TEM, XRD, and IR. They then used the materials as efficient photocatalysts to destroy dyes. They applied reactions and knowledge they had learned in their chemistry courses. They learned to solve problems by finding new ways to synthesize or characterize their compounds. They learned to run, fix, and change settings on multifaceted instruments. They learned to trouble-shoot problems to solve instrumental errors. They learned to reduce human error and understand …

Organic Synthesis As A Platform For Mentoring Undergraduates, Steven L. Castle

Journal of Undergraduate Research

This report summarizes the results that were generated under the auspices of the mentoring environment in my laboratory from January 2014 to the present. A total of six undergraduates participated in the mentoring environment during this period. Their names and accomplishments are listed below.