Chemistry Commons^™

Consumption Profiles Of Illicit And Neuropsychiatric Drugs In Urban And Rural Communities In Kentucky Using Sewage Epidemiology, Tara Croft, Katelyn Foppe, Rhiannon Huffines, Bikram Subedi

Posters-at-the-Capitol

The drug overdose deaths in the USA increased by ~20% from 2015 to 2016 to the total >63,600 drug overdose deaths in 2016. Kentucky is among the highest rate of drug overdose death states in the USA. The current estimates of the prevalence of substance abuse are based on the self-reported surveys, overdose/toxicological reports, and drug-related crime statistics. Survey-based conventional approaches are not only cost and time-intensive but also underestimate the actual consumption of drugs. As “wastewater never lie,” the drug residues in raw wastewater collected from the centralized wastewater treatment plants were utilized to determine the consumption rate of …

Development Of Functional Chemical Probes For The Study Of Viscosity, Fe(Ii), And Ferroptosis And Photo-Triggered Drug Delivery, Yongyi Wei

Chemistry and Chemical Biology ETDs

Small molecule probes are useful tools for the study of biology. In particular, the dye derived fluorescence probes enable to spatiotemporally monitor the events of analytes of interest. The noninvasive feature is particularly attractive for the biological studies in live cells. The challenge is to develop chemical probes capable of detection of the analyte of interest with high specificity.

Toward this end, my Ph. D. study centers on the development of novel chemical probes for the study and understanding of the alternation of important cellar contents and substances and their functions and relationship between normal and disease states. In the …

Crystallographic And Computational Characterization Of Methyl Tetrel Bonding In S-Adenosylmethionine-Dependent Methyltransferases, Raymond C. Trievel, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Tetrel bonds represent a category of non-bonding interaction wherein an electronegative atom donates a lone pair of electrons into the sigma antibonding orbital of an atom in the carbon group of the periodic table. Prior computational studies have implicated tetrel bonding in the stabilization of a preliminary state that precedes the transition state in S_N2 reactions, including methyl transfer. Notably, the angles between the tetrel bond donor and acceptor atoms coincide with the prerequisite geometry for the S_N2 reaction. Prompted by these findings, we surveyed crystal structures of methyltransferases in the Protein Data Bank and discovered …

Micro-Flow Nanocatalysis: Synergic Effect Of Tfoh@Spions And Micro-Flow Technology As An Efficient And Robust Catalytic System For The Synthesis Of Plasticizers, Maryam Tashi, Behnaz Shafiee, Yoshie Sakamaki, Ji-Yun Hu, Zachary Heidrick, Ahmad R. Khosropour, M. Hassan Beyzavi

Chemistry & Biochemistry Faculty Publications and Presentations

The combination of continuous flow technology with immobilizing of only 0.13 mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h−1 compared to 403.8 to 3099 h−1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.

Spatial Variation In Throughfall, Soil, And Plant Water Isotopes In A Temperate Forest, Gregory R. Goldsmith, Scott T. Allen, Sabine Braun, Nadine Engbersen, Clara Romero González-Quijano, James W. Kirchner, Rolf T. W. Siegwolf

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Studies of stable isotopes of water in the environment have been fundamental to advancing our understanding of how water moves through the soil‐plant‐atmosphere continuum; however, much of this research focuses on how water isotopes vary in time, rather than in space. We examined the spatial variation in the δ¹⁸O and δ²H of throughfall and bulk soil water, as well as branch xylem and bulk leaf water of Picea abies (Norway Spruce) and Fagus sylvatica (Beech), in a 1 ha forest plot in the northern Alps of Switzerland. Means and ranges of water isotope ratios varied considerably …

Structure-Based Design, Synthesis And Applications Of A New Class Of Peptidomimetics: 'Y-Aa Peptides And Their Derivatives, Ma Su

USF Tampa Graduate Theses and Dissertations

Peptidomimetics can mimic hierarchical structures of peptides and proteins. Thus, they are extensively studied for therapeutic applications. To break the limitation of backbones and frameworks and expand the peptidomimetics family, a new class of peptidomimetics - “γ-AApeptides” was developed. Design of γ-AApeptides is based on the chiral peptide nucleic acids (PNAs) backbone.

The World Health Organization estimates that one -third of all deaths in the world are on account of infectious diseases. AMPs are important because of their high activity against broad spectrum microbes, less susceptible to grow resistance and selectivity in binding to bacterial cells over human cells. γ-AApeptides …

The Legendre Transformation For Beginning Thermodynamics Students, Carl W. David

Chemistry Education Materials

The Legendre Transform, as traditionally taught in introductory Physical Chemistry classes, can be better understood with some simple examples, which are discussed herein.

Synthesis And Evaluation Of Troponoids As A New Class Of Antibiotics, Feng Cao, Cari Orth, Maureen J. Donlin, Patrick Adegboyega, Marvin J. Meyers, Ryan P. Murelli, Mohamed Elagawany, Bahaa Elgendy, John E. Tavis

Publications and Research

Novel antibiotics are urgently needed. The troponoids [tropones, tropolones, and α-hydroxytropolones (α-HT)] can have anti-bacterial activity. We synthesized or purchased 92 troponoids and evaluated their antibacterial activities against Staphylococcus aureus, Escherichia coli, Acinetobacter baumannii, and Pseudomonas aeruginosa. Preliminary hits were assessed for minimum inhibitory concentrations (MIC80) and cytotoxicity (CC50) against human hepatoma cells. Sixteen troponoids inhibited S. aureus/E. coli/ A. baumannii growth by ≥80% growth at <30 >μM with CC50 values >50 μM. Two selected tropolones (63 and 285) inhibited 18 methicillin-resistant S. aureus (MRSA) strains with similar MIC80 values as against a reference strain. Two selected thiotropolones (284 and 363) …

Are The Oxygen Isotope Values Of The Late Cretaceous Western Interior Seaway Different From The Open Ocean?, Camille H. Dwyer, Corinne Myers, Viorel Atudorei

Shared Knowledge Conference

The Western Interior Seaway (WIS) was a North American epicontinental sea that was connected to the open ocean through the passage of the northern Boreal Sea and the southern Tethys Sea from the early Albian (~113 million years ago) to the early Paleogene (~65 million years ago). The WIS began to recced and lost its connection to the southern Tethys Sea in the late Campanian (~72 million years ago). In the early Paleogene, the WIS dried up completely. The oxygen isotopic composition (δ18O) of benthic bivalves was measured from the upper Campanian and lower Maastrichtian (75 million years ago to …

Catalytic Deoxygenation Of Model And Realistic Feeds To Fuel-Like Hydrocarbons Over Supported Nickel-Copper Catalysts, Deyshon Ward, Kazi Javed

Posters-at-the-Capitol

The goal was to make a renewable fuel by using catalysts to remove oxygen molecules from fats. This is a current issue that society faces today because nonrenewable fossil fuels hurt the environment more than they help it. There are two components that make up a heterogeneous catalyst, a support and a reduced metal active phase. The active metal phases Nickel, Palladium, Platinum have been studied in the past on an alumina and carbon supports. We were investigating other supports using Nickel as the active phase component to determine the effect the support has on the catalyst removing oxygen of …

An In Vitro Study On Skin Protection Across The Uv Spectra, Cheyenne Boone

Posters-at-the-Capitol

Skin cancer is the number one cancer in the United States. Lack of awareness of how harmful UV radiation is could be the cause of the over two million cases reported since 2012. It appears that there is not a lot information on the active ingredients used in sunscreens. Some of the compounds have been linked to birth defects, hormone disruptions, and the bleaching of coral reefs. Samples of commonly used sunscreens (both sprays and creams), cosmetic foundation, essential oils, lotions, and three pure organic actives were tested at specific concentrations and ran through a UV spectrometer. The results have …

Evidence For A Partially Stalled Γ Rotor In F, Angela Murcia Rios, Siavash Vahidi, Stanley D Dunn, Lars Konermann

Chemistry Publications

F₁-ATPase uses ATP hydrolysis to drive rotation of the γ subunit. The γ C-terminal helix constitutes the rotor tip that is seated in an apical bearing formed by α₃β₃. It remains uncertain to what extent the γ conformation during rotation differs from that seen in rigid crystal structures. Existing models assume that the entire γ subunit participates in every rotation. Here we interrogated E. coli F₁-ATPase by hydrogen-deuterium exchange (HDX) mass spectrometry. Rotation of γ caused greatly enhanced deuteration in the γ C-terminal helix. The HDX kinetics implied that most F_{1 …}

Enzyme Kinetics From Circular Dichroism Of Insulin Reveals Mechanistic Insights Into The Regulation Of Insulin-Degrading Enzyme, Valerie A. Ivancic, Claire A. Krasinski, Qiuchen Zheng, Rebecca J. Meservier, Donald E. Spratt, Noel D. Lazo

Chemistry

Insulin-degrading enzyme (IDE) is a zinc metalloprotease that selectively degrades biologically important substrates associated with type 2 diabetes and Alzheimer's disease (AD). As such, IDE is an attractive target for therapeutic innovations. Amajor requirement is an understanding of how other molecules present in cells regulate the activity of the enzyme toward insulin, IDE's most important physiologically relevant substrate. Previous kinetic studies of the IDE-dependent degradation of insulin in the presence of potential regulators have used iodinated insulin, a chemical modification that has been shown to alter the biological and biochemical properties of insulin. Here, we present a novel kinetic assay …

Intranasal Rapamycin Ameliorates Alzheimer-Like Cognitive Decline In A Mouse Model Of Down Syndrome, Antonella Tramutola, Chiara Lanzillotta, Eugenio Barone, Andrea Arena, Ilaria Zuliani, Luciana Mosca, Carla Blarzino, D. Allan Butterfield, Marzia Perluigi, Fabio Di Domenico

Chemistry Faculty Publications

Background: Down syndrome (DS) individuals, by the age of 40s, are at increased risk to develop Alzheimer-like dementia, with deposition in brain of senile plaques and neurofibrillary tangles. Our laboratory recently demonstrated the disturbance of PI3K/AKT/mTOR axis in DS brain, prior and after the development of Alzheimer Disease (AD). The aberrant modulation of the mTOR signalling in DS and AD age-related cognitive decline affects crucial neuronal pathways, including insulin signaling and autophagy, involved in pathology onset and progression. Within this context, the therapeutic use of mTOR-inhibitors may prevent/attenuate the neurodegenerative phenomena. By our work we aimed to rescue mTOR signalling …

Kinetic Characterization Of The Shigella Type Three Secretion System Atpase Spa47 Using Α-32p Atp, Heather B. Case, Nicholas E. Dickenson

Chemistry and Biochemistry Faculty Publications

ATPases represent a diverse class of enzymes that utilize ATP hydrolysis to support critical biological functions such as driving ion pumps, providing mechanical work, unfolding/folding proteins, and supporting otherwise thermodynamically unfavorable chemical reactions. We have recently shown that the Shigella protein Spa47 is an ATPase that supports protein secretion through its specialized type three secretion apparatus (T3SA), supporting infection of human host cells. Characterizing ATPases, such as Spa47, requires a means to accurately determine enzyme activity (ATP hydrolysis) as a function of time, reaction conditions, and potential cofactors, regulators, inhibitors, etc. Here, we describe a detailed protocol for characterizing …

Application Of Click Chemistry In The Development Of Peptide Based Hiv Fusion Inhibitors, Mukesh Madan Mudgal, Nagaraju Birudukota

Chemistry and Physics Faculty Articles

Human Immunodeficiency Virus (HIV) continues to be a major global public health issue. Inhibition of HIV envelope fusion with the CD4 cell membrane prevents the entry of HIV into the CD4 cells providing a novel approach to the treatment of HIV infection. Thus, interference in the fusion of the virus with the co-receptor substrate appears to be a specific and potential way to fight HIV infection and replication. Applications of click chemistry are spreading in the field of drug discovery and it became a powerful tool for the synthesis of medicinally important compounds.

Remarkably, the Cu (I)-Catalyzed Azide-Alkyne Cycloaddition (CuAAC) …

Analysis And New Applications Of Metal Organic Frameworks (Mof): Thermal Conductivity Of A Perovskite-Type Mof And Incorporation Of A Lewis Pair Into A Mof., Wilarachchige D C B Gunatilleke

USF Tampa Graduate Theses and Dissertations

Metal organic frameworks have gained much attention due to their tunable pore sizes and very high surface areas. With the discovery many of these type materials the need has raised to look into new applications of theses porous frameworks. This thesis focuses on the synthesis of a new perovskite-type metal organic framework and measurement of its thermal conductivity in search of its applicability as a thermoelectric material. The second part of this work focuses on the synthesis of a metal organic framework incorporated with a Lewis pair for the first time. The optimum loading amount of the Lewis pair into …

Characterization And Effect Of Metal Ions On The Formation Of The Thermus Thermophilus Sco Mixed Disulfide Intermediate, Liezelle C. Lopez, Nikita Mukhitov, Lindsey D. Handley, Cristina S. Hamme, Cristina R. Hofman, Lindsay Euers, Jennifer R. Mckinney, Amani D. Piers, Ellen Wadler, Laura M. Hunsicker-Wang

Chemistry Faculty Research

The Sco protein from Thermus thermophilus has previously been shown to perform a disulfide bond reduction in the Cu_A protein from T. thermophilus, which is a soluble protein engineered from subunit II of cytochrome ba ₃ oxidase that lacks the transmembrane helix. The native cysteines on TtSco and TtCu_A were mutated to serine residues to probe the reactivities of the individual cysteines. Conjugation of TNB to the remaining cysteine in TtCu_A and subsequent release upon incubation with the complementary TtSco protein demonstrated the formation of the mixed disulfide intermediate. The cysteine of …

Scaling Nonreactive Cross Flow Over A Heated Plate To Simulate Forest Fires, Nikolay Gustenyov, Nelson Akafuah, Ahmad Salaimeh, Mark A. Finney, Sara Mcallister, Kozo Saito

Institute of Research for Technology Development Faculty Publications

The paper reports visualization of the flow of smoke over a flat surface inside of a low-speed wind tunnel. A heating plate flush mounted on the wind tunnel floor simulated a spreading line fire that produces uniform heat flux under constant wind speed condition. A paper-thin cloth was soaked with commercially available Vaseline and placed on top of the heating plate; when it is heated, it produced thick white smoke, ideal for flow visualization. Two sides and top of the wind tunnel were made of a trans- parent acrylic sheet that enabled LED and laser sheet light illumination of the …

Interactions Between Spermine-Derivatized Tentacle Porphyrins And The Human Telomeric Dna G-Quadruplex, Navin C. Sabharwal , '14, Jessica Chen , '17, Joo Hyun Lee , '17, C. M. A. Gangemi, A. D'Urso, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

G-rich DNA sequences have the potential to fold into non-canonical G-Quadruplex (GQ) structures implicated in aging and human diseases, notably cancers. Because stabilization of GQs at telomeres and oncogene promoters may prevent cancer, there is an interest in developing small molecules that selectively target GQs. Herein, we investigate the interactions of meso-tetrakis-(4-carboxysperminephenyl)porphyrin (TCPPSpm4) and its Zn(II) derivative (ZnTCPPSpm4) with human telomeric DNA (Tel22) via UV-Vis, circular dichroism (CD), and fluorescence spectroscopies, resonance light scattering (RLS), and fluorescence resonance energy transfer (FRET) assays. UV-Vis titrations reveal binding constants of 4.7 × 10⁶ and 1.4 × 10⁷ M⁻¹ and binding stoichiometry of …

Lc-Ms/Ms Based Analysis Of Vitamins B3 And B6 In Healthy And Obese Emirati Population, Ghada Rashad Mohamed

Theses

Water-soluble vitamins like Vitamin B3, B6, and B9 are of utmost importance in human health and disease, as they are involved in numerous critical metabolic reactions. Not surprisingly, deficiencies of these vitamins have been linked to various disease states. For example, Vitamin B6 deficiency has been related to many diseases in humans especially in women with type 1 diabetes and in patients with systemic inflammation, liver disease, rheumatoid arthritis, and those infected with HIV. Similarly, derivatives of Vitamin B9 (such as folates), are needed to synthesize, repair, and methylate DNA as well as to act as a cofactor in certain …

Hot Spots And Hot Moments Of Soil Moisture Explain Fluctuations In Iron And Carbon Cycling In A Humid Tropical Forest Soil, Diego Barcellos, Christine S. O'Connell, Whendee L. Silver, Christof Meile, Aaron Thompson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Soils from humid forests undergo spatial and temporal variations in moisture and oxygen (O₂) in response to rainfall, and induce changes in iron (Fe) and carbon (C) biogeochemistry. We hypothesized that high rainfall periods stimulate Fe and C cycling, with the greatest effects in areas of high soil moisture. To test this, we measured Fe and C cycling across three catenas at valley, slope, and ridge positions every two days for a two-month period in a rainforest in Puerto Rico. Over 12 days without rain, soil moisture, Fe^II, rapidly reducible Fe oxides (Fe^III_RR), …

Synthesis And Biological Evaluation Of Phaeosphaeride A Derivatives As Antitumor Agents, Victoria Abzianidze, Petr Beltyukov, Sofya Zakharenkova, Natalia Moiseeva, Jennifer Mejia, Alvin Holder, Yuri Trishin, Alexander Berestetskiy, Victor Kuznetsov

Chemistry & Biochemistry Faculty Publications

New derivatives of phaeosphaeride A (PPA) were synthesized and characterized. Anti-tumor activity studies were carried out on the HCT-116, PC3, MCF-7, A549, К562, NCI-Н929, Jurkat, THP-1, RPMI8228 tumor cell lines, and on the HEF cell line. All of the compounds synthesized were found to have better efficacy than PPA towards the tumor cell lines mentioned. Compound 6 was potent against six cancer cell lines, HCT-116, PC-3, K562, NCI-H929, Jurkat, and RPMI8226, showing a 47, 13.5, 16, 4, 1.5, and 7-fold increase in anticancer activity comparative to those of etoposide, respectively. Compound 1 possessed selectivity toward the NCI-H929 cell line (IC …

Mass Spectrometry And Nuclear Magnetic Resonance In The Chemometric Analysis Of Cellular Metabolism, Eli Riekeberg

Department of Chemistry: Dissertations, Theses, and Student Research

The development and awareness of Machine Learning and “big data” has led to a growing interest in applying these methods to bioanalytical research. Methods such as Mass Spectrometry (MS), and Nuclear Magnetic Resonance (NMR) can now obtain tens of thousands to millions of data points from a single sample, due to fundamental instrumental advances and ever-increasing resolution. Simple pairwise comparisons on datasets of this magnitude can obfuscate more complex underlying trends, and does a disservice to the richness of information contained within. This necessitates the need for multivariate approaches that can more fully take advantage of the complexity of these …

Bio-Inspired Polydopamine Surface Modification Of Nanodiamonds And Its Reduction Of Silver Nanoparticles, Yun Zeng, Wenyan Liu, Risheng Wang

Chemistry Faculty Research & Creative Works

Surface functionalization of nanodiamonds (NDs) is still challenging due to the diversity of functional groups on the ND surfaces. Here, we demonstrate a simple protocol for the multifunctional surface modification of NDs by using mussel-inspired polydopamine (PDA) coating. In addition, the functional layer of PDA on NDs could serve as a reducing agent to synthesize and stabilize metal nanoparticles. Dopamine (DA) can self-polymerize and spontaneously form PDA layers on ND surfaces if the NDs and dopamine are simply mixed together. The thickness of a PDA layer is controlled by varying the concentration of DA. A typical result shows that a …

Crystal Structure Of The 13-(E)-(2-Aminobenzylidene)-Parthenolide, Shobanbabu Bommagani, Narsihma R. Penthala, Sean Parkin, Peter A. Crooks

Chemistry Faculty Publications

The title compound, C₂₁H₂₅NO₃ [systematic name: (1aR,4E,7aS,8E,10aS,10bR)-8-(2-amino­benzyl­idene)-1a,5-dimethyl-2,3,6,7,7a,8,10a,10b-octa­hydro­oxireno[2′,3′:9,10]cyclo­deca­[1,2-b]furan-9(1aH)-one], was synthesized by the reaction of parthenolide [systematic name (1aR,7aS,10aS,10bS,E)-1a,5-dimethyl-8-methyl­ene-2,3,6,7,7a,8,10a,10b-octa­hydro­oxireno[2′,3′:9,10]cyclo­deca­[1,2-b]furan-9(1aH)-one] with 2-iodo­aniline via Heck reaction conditions. The mol­ecule is composed of fused ten-, five- (lactone), and three-membered (epoxide) rings. The lactone ring shows a flattened envelope-type conformation (r.m.s. deviation from planarity = 0.0477 Å), and bears a 2-amino­benzyl­idene substituent that is disordered over two conformations [occupancy …

Development Of Hydroxyapatite-Polymer Sorbents For The Removal Of Heavy Metal Ions From Waste Waters, Eleanora Charnetskaya

Chemistry Theses

Water pollution due to the presence of soluble metal ions is one of the greatest challenges to environmental scientists. Different methods have been explored to the removal of these soluble ions. Among these methods, elimination by sorption into/onto solid materials has been considered one of the successful approaches. Sorbent materials usually chemically interact with soluble ions and eliminate them by bond formation between the ions and the sorbent molecules. On the other hand, soluble ions can be also exchanged with inorganic sorbents in which other environmentally friendly ions can exchange with the soluble metal ions. In the current study, the …

Development, Characterization And Application Of Multi-Detector Flow Injection Systems Based On A Serial Flow Configuration For Simultaneous Multianalyte Determination, Aisha Rashed Al Hameidi Yammahi

Chemistry Theses

Oxidase enzymes have been used successfully in the analysis of several biochemical species such as glucose, lactate, pyruvate, creatine, creatinine, amino acids, cholesterol and sialic acid, by generating - in a single or consecutive reaction -hydrogen peroxide (H₂O₂) as a signal molecule which is commonly detected amperometrically. Some approaches have been also reported to use more than one enzyme in a given system to achieve multi-analyte determination. This study aims to evaluate a novel approach for n-analyte determination based on n-enzyme reactors (each is loaded with one or more oxidase enzyme) as well as n-1 catalase immobilized …

Sequestration Effect On The Open-Cyclic Switchable Property Of Warfarin Induce By Cyclodextrin: Time-Resolved Fluorescence Study, Naji Saleh Al-Dubaili

Chemistry Theses

In this work, the photophysical properties of the fluorescent anticoagulant drug warfarin (W) were examined in water and inside methyl-β-cyclodextrins (Me-β- CD) through absorption and time-resolved fluorescence measurements at pH 3 and 9 and upon the selective excitation of different isomers of warfarin at 280 and 320 nm. The values of binding constants (2.9 × 10³ M^–1 and 4.2 × 10² M^–1 for protonated and deprotonated forms, respectively) were extracted from the spectrophotometric data. Both absorption and time-resolved fluorescence results established that the interior of the macromolecular host binds preferentially the open protonated form, red shifts …

Development And Characterization Of A Portable Apparatus For Continuous Measurement Of Hydrogen Sulfide In Gas Streams, Bashar Yousef Abu Hattab

Chemistry Theses

A novel detection scheme for the hydrogen sulfide (H₂S) was described and patented recently by researchers at UAE University. This detection scheme and the described bench-scale analyzer offered the advantage of low-cost solution for real-time monitoring of percentile levels of H₂S with excellent signal stability. However, this previous work suffered from two major limitations, which are the relatively low sensitivity and slow response time, which mainly hindered its commercial utilization. Therefore, the aims of the present work were to enhance the detection sensitivity, decrease the response time, and develop a portable prototype of the H₂S analyzer based on the improved …