Chemistry Commons^™

Peptide Corrination For The Mitigation Of Nausea And Emesis In The Treatment Of Type 2 Diabetes, Ian Tinsley

Dissertations - ALL

This thesis addresses several questions focused on the activation of receptors expressed withinthe area postrema (AP) and the nucleus tractus solitarius (NTS), regions known to influence nausea and emesis. Prevention of such effects were achieved via corrination, covalent attachment to vitamin B12 (B12) or other corrin constructs, of GLP glucagon-like peptide-one (GLP-1) receptor (GLP-1R) agonists or via the use of GRASP a growth differentiation factor 15 (GDF15) glial derived neurotropic family receptor α-like (GFRAL) complex antagonist.

Stereocontrolled Mannosylation By Hydrogen-Bond-Mediated Aglycone Delivery, Catherine Alex

Dissertations

Stereocontrolled Mannosylation by Hydrogen-Bond-Mediated Aglycone Delivery

Carbohydrates are the essential bio-molecules of life as they form the forefront of interactions with receptors, proteins, pathogens, or neighboring cells. On cell-surfaces, carbohydrates are mostly found as linear or branched glycoconjugates, and a majority of them are linked via either 1,2-cis or 1,2-trans O-glycosidic linkages. There is no template-driven pathway for achieving the synthesis of glycans unlike other biomolecules like proteins and nucleic acids. The synthesis of 1,2-trans glycosides can be reliably achieved via the neighboring group assistance. The synthesis of 1,2-cis glycosides is difficult because, beyond weak anomeric effects, there are …

Aromatic Substitution: Another View, Charles A. Kingsbury

Department of Chemistry: Faculty Publications

Electrophilic substitution on substituted benzenes is reviewed in terms of molecular orbitals. The HOMO falls into two classes. For all meta director C-X groups, a node passes through the ring and through the substituent C-X bond. With ortho/para director C-X groups, a node perpendicular to the one described above, passes through the ortho-meta bonds.

Enrolling Reactive Oxygen Species In Photon-To-Chemical Energy Conversion: Fundamentals, Technological Advances, And Applications, Irving D. Rettig, Theresa M. Mccormick

Chemistry Faculty Publications and Presentations

In theory, oxygen (O2) is an ideal chemical reagent because of its high relative abundance and negligible environmental toxicity. In practice however, by the nature of its ground state electronic configuration, many chemical reactions involving O2 are spin forbidden which dramatically decreases its reactivity and thus its utility in applications. More reactive forms of O2 can be achieved by changing its electronic configuration through the use of photochemical and photophysical methods. This review highlights the roll of photon-to-chemical energy conversion in two of these reactive oxygen species (ROS): superoxide (O2−) and singlet oxygen (1O2), which can be accessed through a …

Petrology And Geochemistry Of Evolved Achondrites: Planetesimal Mantles And Crusts, Zoltan Vaci

Earth and Planetary Sciences ETDs

Melting and differentiation are fundamental to early solar system evolution on planetary bodies that accreted enough material to heat up radioactively or through impacts and breach their solidi. Partially and fully melted material is present in the meteorite record in the form of primitive achondrites and achondrites, which are fragments of planetesimals that underwent heating events in the first few million years of solar system history. Although the vast majority of this material is mafic or ultramafic, new evolved samples, recovered in the last few decades, are pushing the petrologic and geochemical boundaries of planetesimal melting, differentiation, and crust formation. …

Photovoltages In Polycrystalline Mosaic Solar Cells, Steluta A. Dinca, Eric A. Schiff

Chemistry - All Scholarship

In some thin-film solar cells the light-absorbing layer is a mosaic of crystalline grains whose boundaries run from the back to the front of the cell. We used the semiconductor modeling software Sesame to do numerical calculations of the optoelectronic properties of such cells assuming that recombination of minority photocarriers occurs primarily at the grain boundaries. The work complements analytical results for diffusion-limited recombination at grain boundaries and dislocations. We chose idealized n-CdS/p-CdTe solar cells for illustration. We find that the open-circuit voltage, V_oc, under illumination declines logarithmically with increasing ratio D/θ², where D is the …

Structures Of Rhodopsin In Complex With G-Protein-Coupled Receptor Kinase 1, Qiuyan Chen, Manolo Plascencia, Zhuang Li, Somnath Mukherjee, Dhabaleswar Patra, Chun-Liang Chen, Thomas Klose, Xin-Qiu Joe Yao, Anthony A. Kossiakoff, Leifu Chang, Philip C. Andrews, John J.G. Tesmer

Chemistry Faculty Publications

G-protein-coupled receptor (GPCR) kinases (GRKs) selectively phosphorylate activated GPCRs, thereby priming them for desensitization1. Although it is unclear how GRKs recognize these receptors2,3,4, a conserved region at the GRK N terminus is essential for this process5,6,7,8. Here we report a series of cryo-electron microscopy single-particle reconstructions of light-activated rhodopsin (Rho*) bound to rhodopsin kinase (GRK1), wherein the N terminus of GRK1 forms a helix that docks into the open cytoplasmic cleft of Rho*. The helix also packs against the GRK1 kinase domain and stabilizes …

Experimental Evidence That Metapopulation Structure Can Accelerate Adaptive Evolution, Partha Pratim Chakraborty, Louis R. Nemzer, Rees Kassen

Chemistry and Physics Faculty Articles

Whether the spatial arrangement of a population influences adaptive evolution has been a long-standing question in population genetics. In contrast to standard population genetic models, evolutionary graph theory (EGT) predicts certain topologies amplify (increase) the probability that a beneficial mutation will spread in the population relative to a well-mixed population. Here, we test these predictions empirically by tracking the fixation dynamics of an antibiotic resistant mutant under positive selection as it spreads through networks of different topologies both in vitro and in silico. We show that star-like topologies involving bi-directional dispersal between a central hub and peripheral leaves can …

Catalytic Transfer Deuteration And Hydrodeuteration: Emerging Techniques To Selectively Transform Alkenes And Alkynes To Deuterated Alkanes, Zoua Pa Vang, Samuel J. Hintzsche, Joseph R. Clark

Chemistry Faculty Research and Publications

Increasing demand for deuterium-labeled organic molecules has spurred a renewed interest in selective methods for deuterium installation. Catalytic transfer deuteration and transfer hydrodeuteration are emerging as powerful techniques for the selective incorporation of deuterium into small molecules. These reactions not only obviate the use of D₂ gas and pressurized reaction setups but provide new opportunities for selectively installing deuterium into small molecules. Commercial or readily synthesized deuterium donors are typically employed as easy-to-handle reagents for transfer deuteration and hydrodeuteration reactions. In this minireview, recent advances in the catalytic transfer deuteration and hydrodeuteration of alkenes and alkynes for the selective …

Insight Into The Acrab-Tolc Complex Assembly Process Learned From Competition Studies, Prasangi Rajapaksha, Isoiza Ojo, Ling Yang, Ankit Pandeya, Thilini Abeywansha, Yinan Wei

Chemistry Faculty Publications

The RND family efflux pump AcrAB-TolC in E. coli and its homologs in other Gram-negative bacteria are major players in conferring multidrug resistance to the cells. While the structure of the pump complex has been elucidated with ever-increasing resolution through crystallography and Cryo-EM efforts, the dynamic assembly process remains poorly understood. Here, we tested the effect of overexpressing functionally defective pump components in wild type E. coli cells to probe the pump assembly process. Incorporation of a defective component is expected to reduce the efflux efficiency of the complex, leading to the so called “dominant negative” effect. Being one of …

Ganglioside Alters Phospholipase Trafficking, Inhibits Nf-Κb Assembly, And Protects Tight Junction Integrity, John J. Miklavcic, Qun Li, Jordan Skolnick, Alan B. R. Thomson, Vera C. Mazurak, Michael Tom Clandinin

Food Science Faculty Articles and Research

Background and Aims: Dietary gangliosides are present in human milk and consumed in low amounts from organ meats. Clinical and animal studies indicate that dietary gangliosides attenuate signaling processes that are a hallmark of inflammatory bowel disease (IBD). Gangliosides decrease pro-inflammatory markers, improve intestinal permeability, and reduce symptoms characteristic in patients with IBD. The objective of this study was to examine mechanisms by which dietary gangliosides exert beneficial effects on intestinal health.

Methods: Studies were conducted in vitro using CaCo-2 intestinal epithelial cells. Gangliosides were extracted from milk powder and incubated with differentiated CaCo-2 cells after exposure to pro-inflammatory stimuli. …

Tp-5801 In Vitro Kinase Screen Data, Joshua Andersen

ScholarsArchive Data

In vitro kinase screen data for TP-5801 to accompany Chan and Egbert et al., Nature Communications, 2021 (in press)

Gate-Tunable Optical Extinction Of Graphene Nanoribbon Nanoclusters, Erin Sheridan, Gang Li, Mamun Sarker, Shan Hao, Ki-Tae Eom, Chang-Beom Eom, Alexander Sinitskii, Patrick Irvin, Jeremy Levy

Department of Chemistry: Faculty Publications

We investigate the optical response of graphene nanoribbons (GNRs) using the broadband nonlinear generation and detection capabilities of nanoscale junctions created at the LaAlO₃/SrTiO₃ interface. GNR nanoclusters measured to be as small as 1–2 GNRs in size are deposited on the LaAlO₃ surface with an atomic force microscope tip. Time-resolved nonlinear optical probes of GNR nanoclusters reveal a strong, gate-tunable second and third harmonic response, as well as strong extinction of visible to near-infrared light at distinct wavelengths, similar to previous reports with graphene.

Preparation And Characterization Of Single Layer Conducting Polymer Electrochromic And Touchchromic Devices, Sharan Kumar Indrakar

USF Tampa Graduate Theses and Dissertations

Electrochromic devices (ECDs) have triggered great interest because of their potential applicability in energy-efficient buildings and low power display systems, including reflective type smart windows/mirrors and wearable-flexible devices. In the past decades, electrochromic technologies with different device structures and materials have been proposed. The idea of employing a simple device structure with a durable, cost effective electrolyte is crucial to designing and manufacturing high-performance ECDs. With this idea in mind, this thesis describes the various efforts to develop a simple ECD comprising of a composite single active layer gel electrolyte, sandwiched between two transparent conducting electrodes, lasting over 10,000 cycles …

Electrochemical Reduction Of Hexavalent Chromium In Acetonitrile Using Glassy Carbon Electrodes, Temitope Jegede

LSU Master's Theses

Hexavalent chromium Cr(VI), a form of chromium mainly generated through industrial processes, has attracted great research interests due to its severe toxicity to biological systems. A common way to remove hexavalent chromium from industrial wastes is through reduction to the non-toxic trivalent state. To this end, methods such as chemical reduction, chemical precipitation and coagulation have been used. However, these methods are limited by poor removal efficiency, formation of secondary pollutants (sludge), and are mostly applicable to aqueous solutions. Recently, electrochemical methods have been investigated for reducing hexavalent chromium, but there is a lack of data on the reduction of …

Local And 2-Local Derivations On Octonion Algebras, Allayar Allambergenov

Karakalpak Scientific Journal

The present paper is devoted to study of local and 2-local derivations on octonion algebras. We shall give a general form of local derivations on the real octonion algebra \[{\mathbb{O}_\mathbb{R}}.\] This description implies that the space of all local derivations on \[{\mathbb{O}_\mathbb{R}}\] when equipped with Lie bracket is isomorphic to the Lie algebra \[\mathfrak{s}{\mathfrak{o}_7}(\mathbb{R})\] of all real skew-symmetric \[7 \times 7\]-matrices. We also consider \[2\]-local derivations on an octonion algebra \[{\mathbb{O}_\mathbb{F}}\] over an algebraically closed field \[\mathbb{F}\] of the characteristic zero and prove that every \[2\]-local derivation on \[{\mathbb{O}_\mathbb{F}}\] is a derivation. Further, we apply these results to similar problems …

Novel “Acid Tuned” Deep Eutectic Solvents Based On Protonated L-Proline, Patrycja Janicka, Andrzej Przyjazny, Grzegorz Boczkaj

Natural Sciences Publications

The paper presents new types of deep eutectic solvents (DESs) based on L-proline protonated using three different acids (hydrochloric, sulfuric and phosphoric)and playing the role of a hydrogen bond acceptor(HBA). Glucose and xylitol were used as hydrogen bond donors (HBD). A series of deep eutectic solvents with various mole ratios were obtained for the systems L-proline: glucose and L-proline: xylitol. Density, melting point, pH and viscosity of the synthesized DESs were determined along with the effect of water content, mole fraction of the HBA in DES and temperature on properties of the DESs. A wide range of densities (1343–1606 kg/m3), …

Functionalized Ionic Liquids For Improved Co2 Hydrogenation Catalysts, Amol Nanduji Jaybhaye

Masters Theses & Specialist Projects

Climate change is one of the biggest problems we are facing today, and anthropogenic greenhouse gases contribute significantly to it. Among greenhouse gasses, carbon dioxide emission is increased drastically and affecting majorly for increasing global temperature, and anything we can do to mitigate carbon dioxide emission will be helpful. A carbon dioxide hydrogenation reaction is a promising technique that can convert carbon dioxide into value-added chemicals, but the reaction rate is slow, and for that, we can use catalysts that will accelerate the reaction rate. Platinum-based nanoparticles have sparked research related to energy and environmental catalysts. Catalytic properties are depending …

Design Of Antioxidant Monomer, Augustine Osilamah Yusuf

Masters Theses & Specialist Projects

Reactive oxygen species such as hydrogen peroxide are present at the sites of inflammation in the body. Degradable polymeric nanoparticles have shown great promise in a range of biomedical applications which include preferential delivery of therapeutics to such inflamed sites. We are working towards a new class of materials expected to have tunable degradation rates in the presence of hydrogen peroxide. These new materials consist of three parts: degradable linkages, antioxidant groups, and unreactive filler monomers such as methylmethacrylate. We have synthesized a polymerization initiator with a degradable linkage, and we have shown that using this initiator to synthesize another …

Stem Afterschool Club - Lava Lamps, Dylan Hiser

Honors Program: Expanded Learning Clubs

Afterschool Club that builds upon what students already know about science with fun and interactive experiments.

Extending Nanoscale Patterning With Multipolar Surface Plasmon Resonances., Issam Kherbouche, Danielle Macrae, Théo Geronimi Jourdain, François Lagugné-Labarthet, Azedine Lamouri, Alexandre Chevillot Biraud, Claire Mangeney, Nordin Félidj

Chemistry Publications

Plasmonic excitation of metallic nanoparticles can trigger chemical reactions at the nanoscale. Such optical effects can also be employed to selectively and locally graft photopolymer layers at the nanostructure surface, and, when combined with a surface functionalization agent, new pathways can be explored to modify the surface of a plasmonic nanoparticle. Among these approaches, diazonium salt chemistry is seen as an attractive strategy due to the high photoinduced reactivity of these salts. In this work, we demonstrate that it is possible to trigger the site-selective grafting of aryl films derived from diazonium salts on distinct nano-localized area of single gold …

Nanozymes—Hitting The Biosensing “Target”, Yingfen Wu, Diane Darland, Julia Zhao

Biology Faculty Publications

Nanozymes are a class of artificial enzymes that have dimensions in the nanometer range and can be composed of simple metal and metal oxide nanoparticles, metal nanoclusters, dots (both quantum and carbon), nanotubes, nanowires, or multiple metal-organic frameworks (MOFs). They exhibit excellent catalytic activities with low cost, high operational robustness, and a stable shelf-life. More importantly, they are amenable to modifications that can change their surface structures and increase the range of their applications. There are three main classes of nanozymes including the peroxidase-like, the oxidase-like, and the antioxidant nanozymes. Each of these classes catalyzes a specific group of reactions. …

Phase-Field Modeling Of The Polymer Membrane Formation Process For Micro- And Ultra-Filtration, Michael Rosario Cervellere

Graduate Theses and Dissertations

Porous polymer membrane filters are widely used in separation and filtration process. Micro- and ultra-filtration membranes are commonly used in biopharmaceutical applications such as filtering viruses and separating proteins from a carrier solution. The formation of these membrane filters via phase inversion is a complex and interconnected process where varying casting conditions can have a wide variety of effects on the final membrane morphol- ogy. Tailoring membrane filters for specific performance characteristics is a tedious and time consuming process. The time and length scales of membrane formation make it extremely difficult to experimentally observe membrane formation. Modeling the membrane formation …

College Of Natural Sciences Newsletter, July 2021, College Of Natural Sciences

College of Natural Sciences Newsletters and Reports

Volume 2, Issue 7.

Page 1 Dean's Message
Page 2 Celebrating Three Years
Page 3 Summer School Travel
Page 4 Media Coverage of CNS
Page 5 Chemistry Teachers Visit
Page 5 Remembering Dr. Warren Hein
Page 6 Research Spotlights: Undergraduate Summer Experiences
Page 7 Open PRAIRIE Data; Grants Awarded in CNS

Ahr Expression On Rorc-Expressing Immune Cells Is Essential For I3c-Mediated Protection Against Colitis, Michal C. Williams

Senior Theses

Colitis is an inflammatory bowel disorder (IBD) whose etiology is attributed to modification in the luminal microbiota and dysregulation in the immune response. Indole is a signaling molecule which is naturally produced by gut luminal microbiota. Indole-3- carbinol (I3C) is a compound commonly found in vegetables and a ligand for the aryl hydrocarbon receptor (AhR). Previous studies have detected decreased expression and activation on the AhR receptor in colitis patients, thought to possibly alter gut microbiota metabolism, subsequently promoting colitis. 1 AhR, expressed in a variety of immune and epithelial cells, contributes to gut homeostasis by affecting vital mediators such …

Chapter 2.2: 3-D Topo Surface Visualization Of Metal Ion Anti-Buffering: An Unexpected Behavior In Metal–Ligand Complexation Systems, Garon C. Smith, Md Mainul Hossain, Daniel D. Barry

Water Topos: A 3-D Trend Surface Approach to Viewing and Teaching Aqueous Equilibrium Chemistry

Diluting a system that contains metal complexes can sometimes cause surprises. This chapter describes “metal ion anti-buffering”, a situation in which free metal ion concentrations rapidly increase as system dilution drives dissociation. It only occurs under excess free ligand conditions when a solution is dominated by higher stoichiometry complexes. The Law of Mass Action is used to provide a mathematical justification for the phenomenon. A Cu²⁺-ethylenediamine mixture exhibits this phenomenon when excess free ethylenediamine (en) is present. For example, it occurs when diluting a solution containing a four-fold excess of en over Cu²⁺. As this mixture …

Structure And Reactivity Of The First Row Transition Metals Bearing Redox-Active Ligands And Tunable H-Bonding Interactions, Khashayar Rajabimoghadam

Chemistry Theses and Dissertations

Metalloenzymes, as natural catalysts, can break a reaction with high activation energy to multiple small reactions with lower activation energies; in these small reactions, multiple bonds form and dissociate rapidly, some metalloenzymes use redox-active ligands in their active site to provide the needed electrons for these multiple small reactions. Additionally, in the secondary coordination sphere in the vicinity of the metalloenzymes, the hydrogen bonding interactions facilitate the transfer and interaction of the substrates and the stabilization of the active intermediates. These unique features in metalloenzymes inspired chemists to design molecular models that can partially mimic the structure and reactivity of …

The Effects Of Sugar Osmolytes On Reverse Micelle Systems, Jenna Deckard, Bridget Gourley Phd

Annual Student Research Poster Session

Reverse Micelles (RM) are nanoscopic pools of water encapsulated by an amphipathic surfactant molecule that allows the water pool to be suspended in a nonpolar solvent. We use RM systems because they allow for the study of water and dissolved osmolyte interactions in confinement. Gaining an understanding of how sugars interact with water in confinement has significant implications for biological systems. This project seeks to understand the effects of galactose as an osmolyte on the interactions, loading limits, and size of RMs when compared to RMs containing only water and RMs containing glucose. Galactose and glucose have slight structural differences, …

Expression Of Lactate Dehydrogenase (Ldha) Wt And A320t Mutant, Natalie Husby, John Csehill, Ian Longen, Ellie Reece, Daniel Gurnon Phd

Annual Student Research Poster Session

The human genome has a length of approximately 3 billion base pairs, containing a total of over 20,000 genes, which can all be subjected to mutations that cause variations in the genome. Variations in a genome can be potentially either benign or pathogenic, but it can be difficult to distinguish whether a variant is one or the other, leading to tens of thousands being classified as variants of unknown significance (VUS). Our lab was particularly interested in the VUSs in lactate dehydrogenase (LDHA), an oxidoreductase enzyme that catalyzes the reversible conversion of pyruvate to lactate, an important component to anaerobic …

Effect Of A Hexylamine Derivative On Cancer Cell Viability, Rachel Delancey, Bamlak Deju, Jeff Hansen Phd, Nipun Chopra Phd

Annual Student Research Poster Session

2-[(p-Chlorophenyl)hydroxymethyl]-1-[(methylamino)hexyl]cyclohexanol is a drug produced by hexyl amine and an epoxide through an aldol epoxidation reaction. Motifs of β-amino alcohols and nonpolar R groups in organic compounds have been found to have cytotoxic properties. Past studies in Dr. Hansen’s lab has shown that this hexylamine derivative has similar LC50 values to other antitumor agents. They also found that the drug was cytotoxic to HL-60 cancer cells. No other cell lines have been tested with this drug. Our study investigates the effect of our compound on varying cell lines to further determine its anticancer properties. Mouse NIH/3T3, Human HEK293, and Human …