Chemistry Commons^™

Structure And Thermodynamics Of Polyglutamine Peptides And Amyloid Fibrils Via Metadynamics And Molecular Dynamics Simulations, Riley Workman

Electronic Theses and Dissertations

Aggregation of polyglutamine (polyQ)-rich polypeptides in neurons is a marker for nine neurodegenerative diseases. The molecular process responsible for the formation of polyQ fibrils is not well understood and represents a growing area of study. To enable development of treatments that could interfere with aggregation of polyQ peptides, it is crucial to understand the molecular mechanisms by which polyQ peptides aggregate into fibrils. Many experimental techniques have been employed to probe polyQ aggregation, however, observations from these studies have not lead to a unified understanding of the properties of these systems, instead yielding competing, fragmented theories of polyQ aggregation. This …

Synthesis Of Modified Biginelli Compounds, Michelle Sarah Collins

Student Theses and Dissertations

The Biginelli reaction has been a distinguished reaction for many years. Their products, the Dihydropyrimidones have been shown to contain a vast array of bioactivity especially when they contain other known bioactive functional groups. Here in we discuss different pathways that these DHPM products can be taken down to combine them with other such bioactive functional groups. We explored the addition of alkene and aldehyde groups to the Biginelli compounds in hopes of synthesizing potential drug candidates. We believe the synthesis of the aldehyde group on the DHPM compounds is a gateway to obtaining the hybrid drug activity we so …

3-Hydroxy-2-(4- Methylphenyl)-4h-Chromen-4-One, Clifford W. Padgett, Will E. Lynch, Kirkland Sheriff, Raven Dean, Sarah Zingales

Chemistry: Faculty Publications (1990-2023)

Our work in the area of carbon-monoxide-releasing mol­ecules led to the synthesis and crystallization of new flavone derivatives as inter­mediates. Herein we report the first crystal structure of the title compound, C16H12O3, a hy­droxy-substituted flavone where the 2-phenyl group has been replaced by a p-tolyl group. The introduction of the 3-hy­droxy group allows the formation of inter­molecular O—H...O=C hydrogen bonds, used to build centrosymmetric R22(10) ring motifs in the crystal.

Fourier Transform Spectroscopy Of The C³Δ-X³Δ Transition Of Tio In Support Of Exoplanet Spectroscopy, James N. Hodges, Peter Bernath

Chemistry & Biochemistry Faculty Publications

Recent limitations in the TiO line list used in cross-correlation detection schemes have made the detection and quantification of TiO in exoplanetary atmospheres challenging. The quality of the line list appears to degrade at wavelengths shorter than 630 nm. The C³Δ-X³Δ electronic transition has strong rovibronic bands near 500 nm. In an effort to improve the line list, a spectrum of TiO in a furnace at 1950 K is analyzed, and the assigned lines of the C³Δ-X³Δ transition are fit with the N² Hamiltonian in the molecular spectrum fitting software, _{PGOPHER …}

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants pK_{a …}

Design And Synthesis Of Circadian Clock Modulators And The Study Of Lov Domain Protein Lkp2 In Arabidosis Thaliana And Brassica Rapa, Aditi Nagar

Chemistry Theses and Dissertations

Circadian rhythms are self-autonomous endogenous clocks synchronized with the rotation of the Earth. With the Earth’s rotation and revolution on its axis, the internal clock undergoes oscillation in the period of ~24 hour and governs day to day activities in most organisms. In humans, it regulates the day to day physiological activities. Today’s modern lifestyle has an impact on health: shift work, jet lag, and irregular eating habits contribute to the misalignment of the endogenous circadian oscillator, thereby, increasing the risk of many metabolic disorders including diabetes, irregular blood pressure, sleep disorders, obesity, depression, and cancer. The primary goal of …

Infra-Red Microwave Spectra, Overtones, Degeneracy And Thermal Populations All In One Diagram, Carl W. David

Chemistry Education Materials

An old drawing, which had an error in it, is re-presented (corrected) for understanding the relationships in diatomic vibrational-rotational interactions at the introductory level.

Platinum@Hexaniobate Nanopeapods: Sensitized Composite Architectures For Photocatalytic Hydrogen Evolution Under Visible Light Irradiation, Clare Davis-Wheeler Chin

LSU New Orleans Theses and Dissertations

Hydrogen fuel is one of the most important areas of research in the field of renewable energy development and production. Hydrogen gas can be generated by fuel cells, water electrolyzers, and heterogeneous nanoscale catalysts. It can be burned to directly release chemical energy or condensed for storage and transport, providing fuel for combustion devices or storing excess energy generated by renewable sources such as wind turbines and concentrated solar power assemblies. While platinum is the most active catalyst for hydrogen reduction, its high cost significantly deters its utilization in advanced photocatalytic materials. One approach to mitigating this expense is optimizing …

Thiophene-Based Molecular Sensors Towards The Selective Detection Of Mercury(Ii) And Other Metals, Austin Kazuo Shigemoto

Dissertations and Theses

This work describes several thiophene-based molecular sensors and various modifications aimed to improve and understand the photophysical and supramolecular properties, such as the association constant (K_a) and selectivity, towards the development of a selective mercury(II) sensor. From the first generation of sensors containing pyridine and thiophene groups, it was determined that thiophene can offer good selectivity for mercury(II) against other transition metal ions, and provide a ratiometric absorption and fluorescent response. The projects following this focused on improving the K_a of the first generation of sensors through several different strategies. Substitution of thiophene for dibenzothiophene was …

Evidence For The Formation Of A Radical-Mediated Flavin-N5 Covalent Intermediate, Yumin Dai, Hannah Valentino, Pablo Sobrado

Chemistry Faculty Research & Creative Works

The redox-neutral reaction catalyzed by 2-haloacrylate hydratase (2-HAH) leads to the conversion of 2-chloroacrylate to pyruvate. Previous mechanistic studies demonstrated the formation of a flavin-iminium ion as an important intermediate in the 2-HAH catalytic cycle. Time-resolved flavin absorbance studies were performed in this study, and the data showed that the enzyme is capable of stabilizing both anionic and neutral flavin semiquinone species. The presence of a radical scavenger decreases the activity in a concentration-dependent manner. These data are consistent with the flavin iminium intermediate occurring by radical recombination.

Fabrication Of Mnox/Mwcnts-Gc Nanocatalyst For Oxygen Evolution Reaction, Yaser M. Asal Mr, Islam M. Al-Akraa Dr, Amr M. Arafa Eng.

Chemical Engineering

Manganese oxide (MnOx) and multiwalled carbon nanotubes (MWCNTs) are intended to modify the GC electrode for oxygen evolution reaction (OER). Optimization of MnOx loading is carried out and the deposition of 55 cycles was sufficient to obtain the highest activity toward OER. The stability of the catalyst is enhanced by the addition of MWCNTs. As a result, an amount of 22 kWh/Kg of O₂ of energy is saved. Several techniques including cyclic voltammetry, linear sweep voltammetry, chronoamperometry, chronopotentiometry, field-emission scanning electron microscopy, and energy dispersive X-ray spectroscopy will be combined to track the catalyst activity and to determine its …

Role Of Stone-Wales Defects On The Interfacial Interactions Among Graphene, Carbon Nanotubes, And Nylon 6: A First-Principles Study, Sanjiv K. Jha, Michael Roth, Guido Todde, J. Paige Buchanan, Robert D. Moser, Manoj K. Shukla, Gopinath Subramanian

Faculty Publications

We investigate computationally the role of Stone-Wales (SW) defects on the interfacial interactions among graphene, carbon nanotubes (CNTs), and Nylon 6 using density functional theory (DFT) and the empirical force-field. Our first-principles DFT calculations were performed using the Quantum ESPRESSO electronic structure code with the highly accurate van der Waals functional (vdW-DF2). Both pristine and SW-defected carbon nanomaterials were investigated. The computed results show that the presence of SW defects on CNTs weakens the CNT-graphene interactions. Our result that CNT-graphene interaction is much stronger than CNT-CNT interaction indicates that graphene would be able to promote the dispersion of CNTs in …

Light Absorption By Polar And Non-Polar Aerosol Compounds From Laboratory Biomass Combustion, Deep Sengupta, Vera Samburova, Chiranjiva Bhattarai, Elena Kirillova, Lynn Mazzoleni, Michealene Iaukea-Lum, Adam Watts, Audrey Khlystov

Department of Chemistry Publications

Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly light-absorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction – brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while …

Ultrafast Laser Filament-Induced Fluorescence Spectroscopy Of Uranyl Fluoride, P. J. Skrodzki, M. Burger, L. A. Finney, F. Poineau, S. M. Balasekaran, J. Nees, K. R. Czerwinski, I. Jovanovic

Chemistry and Biochemistry Faculty Research

Uranyl fluoride (UO2F2) is a compound which forms in the reaction between water and uranium hexafluoride, a uranium containing gas widely used for uranium enrichment. Uranyl fluoride exhibits negligible natural background in atmosphere; as a result, its observation implies the presence and active operation of nearby enrichment facilities and could be used as a tracer for treaty verification technologies. Additionally, detection of UO2F2 has a potential application in guiding remediation efforts around enrichment facilities. Laser-induced fluorescence (LIF) has been proposed in the past as a viable technique for the detection and tracking of UO2F2. We demonstrate that ultrafast laser filamentation …

Examining The Effects Of Amino And Thiolate Ligands On The Reactivity And Selectivity Of Palladium On Carbon In Hydrogenation Reactions, Eric Liu, Christina Li

The Summer Undergraduate Research Fellowship (SURF) Symposium

Heterogeneous catalysts are used widely by chemical and energy industries because they show high reactivity but often suffer from lack of selectivity. On the other hand, ligands are commonly used in homogeneous catalysts to control the reactivity and selectivity; however, the effects of the ligands on the steric and electronic properties of heterogeneous catalysts are less understood. We examine the effects of four different ligands: 1-adamantanethiol, 1-adamantylamine, 1-dodecanethiol, and 1-dodecylamine, for the commercial hydrogenation catalyst palladium on carbon. Hydrogenation reactions are used as a screening tool to see the behavior that the different catalysts exhibit in the presence of unsaturated …

Electronic Effect Of Platinum Alloy Catalysts On Olefin Hydrogenation Kinetics, Colin Reedy, Jeff Miller, Stephen Purdy

The Summer Undergraduate Research Fellowship (SURF) Symposium

Dehydrogenation of alkanes is the first step in transforming light hydrocarbons into liquid fuels and chemicals. This process has traditionally used platinum alloys as catalysts. Alloys are used industrially because they have a greater selectivity than monometallic platinum. Alloying platinum with an inactive promoter modifies the crystalline structure of the surface (geometric effect), and the 5d electrons in platinum responsible for chemistry (electronic effect); both have been suggested to be primarily responsible for dehydrogenation selectivity in platinum alloys. Alloy catalysts have been synthesized using early 3d transition metal promoters with the same Pt₃M crystal structure. X-Ray Absorption Spectroscopy …

Thienoisatin Oligomers As N-Type Molecular Semiconductors, Natalie M. Kadlubowski, Xuyi Luo, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Organic field effect transistors (OFETs) offer many advantages compared to traditional inorganic transistors, such as flexibility and solution processability. In this study we design and synthesize two thienoisatin-based organic semiconducting small molecules, then investigate their electronic properties in n-type OFETs. To introduce n-type charge transport, electron-withdrawing dicarbonitrile moieties were installed on thienoisoindigo and bis-thienoisatin molecules, which led to a quinoidal conjugation on thienoisoindigo, while maintaining an aromatic conjugation on the bis-thienoisatin. Following the syntheses, the molecules were characterized to determine highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels via cyclic voltammetry, as well as any potential …

Alkene Ozonolysis In The Academic Lab, Patrick Dussault

Organic Peroxides: Safety Issues

The following information is offered as a guide based upon our experience with application of ozone for organic oxidations and hydroperoxide synthesis. Please send suggestions, requests, or corrections to [email protected].

Introduction and leading references

Overview of ozonolysis: Mechanism, Substrate reactivity, Typical reaction conditions, Reaction monitoring, Reaction work-ups

Safety Issues

Acknowledgements:

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The following provides a brief introduction to the application of ozonolysis within academic labs. Ozonolysis remains among the most frequently used of methods for oxidative cleavage of alkenes. While best known as a means by which to introduce aldehydes and ketones, ozonolysis can also be used to generate other …

Tof-Sims Analysis Of Plant Seed Interactions With Plant Growth-Promoting Bacteria, Tammy Pheuphong, Rachel Komorek, Xiao-Ying Yu

STAR Program Research Presentations

The use of time-of-flight secondary ion mass spectrometry (ToF-SIMS) in plant biology is a relatively unexplored and quickly developing field. The majority of research in plant SIMS involves the application of ToF-SIMS to study dried wood tissues, and only a handful of studies apply SIMS on plant stems, roots, and/or seeds. Our project provides a brief description and review of previous work using SIMS on plant stems, roots, and/or seeds, along with an emphasis on the sample preparation in each study. Additionally, the use of Brachypodium distachyon (Brachypodium) as a model system for research on grasses has also become more …

Applications Of Diels-Alder Chemistry In Polymer Synthesis, Joshua C. Stambaugh, Philip J. Costanzo, Sierra E. Gosting

STAR Program Research Presentations

Diels-Alder chemistry is utilized for a myriad of commercial applications during polymer synthesis, ranging from self-healing materials to heat responsive materials to emulsion coatings. In particular, the ability to regulate and control the amount and type of functional group linkages is key component for polymer applications. A common strategy that is employed is the use of phenolic maleimide as a dienophile during Diels-Alder synthesis to control the linkages on a polymer, which determines its properties and functionality. This summer was the beginning of a project to prepare a commercial scale, water-based emulsion floor coating/polish. The first step in this project …

Anisotropic Conductive Adhesives For Interdigitated Back Contact (Ibc) Silicon Solar Cells, Katherine M. Lohmuste, Manuel Schnabel, Maikel F.A.M. Van Hest

STAR Program Research Presentations

The current manufacturing process for solar panels using interdigitated back contact (IBC) silicon solar cells involves a multi-step metallization and interconnection process in which a substantial amount of silver is used. This work focuses on a new process using conductive adhesives (CA) which would increase efficiency and lower cost through a one-step metallization and interconnection process that combines with encapsulation using little silver and only requiring metal patterning on the back sheet or back glass. It would also not require direct metallization of the silicon, which would result in fewer defects, while increasing voltage and therefore efficiency. Silver-coated Poly(Methyl Methacrylate) …

Fuel Specific Emissions Trends For In-Use Medium And Heavy-Duty Vehicle Fleets In California, Molly J. Haugen

Electronic Theses and Dissertations

New heavy-duty vehicle regulations have caused significant reductions in hazardous air pollutants, such as particulate matter (PM) and nitrogen oxides (NO_x), due to better engine management and utilization of advanced after-treatment systems. The University of Denver has collected data for gaseous and PM emission measurements from on-road heavy-duty vehicles (HDVs). The On-Road Heavy-Duty Vehicle Emissions Measurement System (OHMS) collected fuel specific emission information on individual HDVs of in-use fleets at two California locations in the spring of 2013, 2015 and 2017. These complimentary fleets, studied over multiple years, produced 7,075 measurements of gaseous and particle emission data providing …

Crystal Structures Of 2-Bromo-1,1,1,3,3,3-Hexa­Methyl-2-(Tri­Methyl­Sil­Yl)Tris­Ilane And 2-Bromo-1,1,1,3,3,3-Hexa­Isopropyl-2-(Triiso­Propyl­Sil­Yl)Tri­Silane, Eva Gulotty, Richard Staples, Shannon Biros, Peter Gaspar, Nigam Rath, William Winchester

Chemistry & Biochemistry Faculty Works

The synthesis and crystal structures of two tris­(tri­alkyl­sil­yl)silyl bromide compounds, C9H27BrSi4 (I, HypSiBr) and C27H63BrSi4 (II, TipSiBr), are described. Compound I was prepared in 85% yield by free-radical bromination of 1,1,1,3,3,3-hexa­methyl-2-(tri­methyl­sil­yl)tris­ilane using bromo­butane and 2,2′-azobis(2-methyl­propio­nitrile) as a radical initiator at 333 K. The mol­ecule possesses threefold rotational symmetry, with the central Si atom and the Br atom being located on the threefold rotation axis. The Si—Br bond distance is 2.2990 (12) Å and the Si—Si bond lengths are 2.3477 (8) Å. The Br—Si—Si bond angles are 104.83 (3)° and the Si—Si—Si bond angles are 113.69 (2)°, reflecting the steric hindrance …

Imaging The Surface Of A Hand-Colored 19th Century Daguerreotype., Madalena S Kozachuk, Maria O Avilés, Ronald R Martin, Brianne Potts, Tsun-Kong Sham, François Lagugné-Labarthet

Chemistry Publications

Daguerreotypes are valued artifacts that constitute a unique historical photographic memory of the 19th century. Understanding their surface chemistry is important in order to conserve and, when necessary, to restore them. Colored highlights were often added by hand to emphasize different features on the daguerreotype's subjects. In the present work, we report on a daguerreotype that was hand-colored with a red pigment that was added to the cheeks of the two individuals. A series of experiments using micro-Raman and micro-Fourier transform infrared spectroscopy and synchrotron-based X-ray fluorescence microscopy and absorption spectroscopy are used to analyze the surface and to determine …

Quercetin Inhibits Glucose Transport By Binding To An Exofacial Site On Glut1, Kathryn E. Hamilton, Janelle F. Rekman, Leesha K. Gunnink, Brianna M. Busscher

University Faculty Publications and Creative Works

Quercetin, a common dietary flavone, is a competitive inhibitor of glucose uptake and is also thought to be transported into cells by GLUT1. In this study, we confirm that quercetin is a competitive inhibitor of GLUT1 and also demonstrate that newly synthesized compounds, WZB-117 and BAY-876 are robust inhibitors of GLUT1 in L929 cells. To measure quercetin interaction with L929 cells, we develop a new fluorescent assay using flow cytometry. The binding of quercetin and its inhibitory effects on 2-deoxyglucose (2DG) uptake showed nearly identical dose dependent effects, with both having maximum effects between 50 and 100 μM and similar …

Manganese Oxide/Hemin-Functionalized Graphene As A Platform For Peroxynitrite Sensing, Haitham F. Kalil, Shaimaa Maher, Tiyash Bose, Mekki Bayachou

Chemistry Faculty Publications

Peroxynitrite (ONOO−, PON) is a powerful oxidizing agent generated in vivo by the diffusion-limited reaction of nitric oxide (NO) and superoxide (O₂˙⁻) radicals. Under oxidative stress, cumulated peroxynitrite levels are associated with chronic inflammatory disorders and other pathophysiological conditions. The accurate detection of peroxynitrite in biological systems is important, not only to understand the genesis and development of diseases, but also to explore and design potential therapeutics. Herein, a manganese oxide/hemin-modified graphene interface is explored as a platform for peroxynitrite amperometric detection. Hemin-functionalized reduced graphene oxide was further modified with manganese oxide nanoparticles to provide a …

Safe Use Of Hydrogen Peroxide In The Organic Lab, Patrick Dussault

Organic Peroxides: Safety Issues

The article describes good practices for use of hydrogen peroxide (H₂O₂) in an organic lab setting. Major headings include:

Leading references; Toxicity; Physical properties; Chemical properties; Stability and incompatibilities; Confinement/pressure; and, References to accidents involving H₂O₂.

Cell-Free Studies Of Catalytic Dna Cleavage By Ruthenium Polypyridyl Complexes (Rpcs) Containing Redox-Active Intercalating Ligands, Enantiomeric Separation And Semi-Prep Scale Purification Of Rpcs, Cynthia Ann Griffith

Chemistry & Biochemistry Dissertations - Archive

Herein, we report the ruthenium (II) polypyridyl complexes (RPCs), [(phen)₂Ru(tatpp)] ²⁺ (3²⁺) and [(phen)₂Ru(tatpp)Ru(phen)₂] ⁴⁺ (4⁴⁺) are shown to cleave DNA in cell-free studies in the presence of a mild reducing agent, i.e. glutathione (GSH), in a manner that is enhanced upon lowering the [O₂] . Reactive oxygen species (ROS) are involved in the cleavage process as hydroxy radical scavengers attenuate the cleavage activity. Cleavage experiments in the presence of superoxide dismutase (SOD) and catalase reveal a central role for H₂O₂ as the immediate precursor for hydroxy radicals. A mechanism is proposed which explains the inverse [O₂] dependence and ROS …

New Methods For Discovery, Fingerprinting, And Analysis Of Cannabis Sativa Natural Products, Allegra Leghissa

Chemistry & Biochemistry Dissertations - Archive

Cannabis sativa is an herbaceous annual that has always been of great interest due to its uses in the manufacturing of textiles and cordage, as well as for its medicinal properties. The two main bioactive components of C. sativa are cannabinoids and terpenes; the former confer the medicinal and pharmaceutical benefits, as well as the psycho-activity, to the plant, while the latter are largely responsible for aroma and flavor. Because of the importance of both sets of analytes, it is crucial to have a comprehensive understanding and characterization of these compounds, and different methods have been developed to address these …

New Strategies For Catalytic C-H And Olefin Hydrosilylation, Parham Asgari

Chemistry & Biochemistry Dissertations - Archive

In the works described here, new catalytic hydrosilylation strategies were explored. First, a highly selective, bond functionalization strategy, achieved via relay of two transition metal catalysts and use of traceless acetal directing groups, was introduced. Specifically, this approach involves the relay of Ir-catalyzed hydrosilylation and Rh-catalyzed ortho-C–H silylation. This acetal directing group strategy was used for catalytic ortho-C–H silylation of phenols and benzoate esters derivatives. Additionally, we developed a transition metal free, catalytic vinyl arenes hydrosilylation method. We describe our discovery on unprecedented, sustainable HAT process and report a mechanism involving Lewis base-catalyzed, complexation-induced HAT (LBCI-HAT), followed by highly selective …