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Effect Of Atypical Protein Kinase C Inhibitor (Dnda) On Cell Proliferation And Migration Of Lung Cancer Cells, Raja Reddy Bommareddy

USF Tampa Graduate Theses and Dissertations

Lung cancer is the second most common cancer, and it is the leading cause of cancer death in both men and women. Elevated levels of PKC-ι and FAK are implicated in the progression of lung cancer and involved in cell proliferation, apoptosis, cell survival, and cell migration processes. Lung cancer diagnosis typically occurs in the late stages, which limits the treatment options. Hence, there is a dire need to develop drugs that are effective and safe to treat lung cancers. We used a novel aPKC inhibitor named DNDA (3,4-amino-2,7 napthalene disulfonic acid) to study the role of atypical PKCs (aPKCs) …

The Activity And Structure Of Cu2+-Biomolecules In Disease And Disease Treatment, Darrell Cole Cerrato

USF Tampa Graduate Theses and Dissertations

Despite its relatively low concentration in the human body, copper is an essential transition metal ion. Under normal circumstances, it is a well-regulated trace element that is introduced via diet or environment depending on the organism. Its strong reactivity and binding to some biologically essential chemicals can be detrimental to the host organism. Herein the oxidative chemistry of copper and its possible prevention in humans and agricultural organisms is discussed, as well as the potential avenues as metal-targeting disease treatment via novel-peptide and peptoid products.

In the first study, copper is implicated in the progression and onset of Alzheimer’s disease. …

Construction Of G-Quadruplexes Via Self-Assembly: Enhanced Stability And Unique Properties, Ying He

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) The construction of well-defined G8-octamers through the monomer conformational design. 2) The construction of cross-layer interactions in the G8-octamer for enhanced stability in H-bond competitive solvents. 3) Design and synthesis of 8-triazole guanosine with photoluminescent properties.

Through the structural conformational design, we have developed a new class of guanosine derivatives with modification on guanine (8-aryl) and ribose (2’,3’-isopropylidene). This unique design has led to the formation of the first discrete G8-octamer with structure characterized by NMR, MS and single crystal X-ray diffraction. The selectivity between monovalent (K+) and divalent cat-ions (Ba2+ and Sr2+) …

Pathological Comparisons Of The Hippocampal Changes In The Transient And Permanent Middle Cerebral Artery Occlusion Rat Models, Fawad Ali Shah, Tao Li, Lina Tariq Al Kury, Alam Zeb, Shehla Khatoon, Gongping Liu, Xifei Yang, Fang Liu, Huo Yao, Arif Ullah Khan, Phil Ok Koh, Yuhua Jiang, Shupeng Li

All Works

© Copyright © 2019 Shah, Li, Kury, Zeb, Khatoon, Liu, Yang, Liu, Yao, Khan, Koh, Jiang and Li. Ischemic strokes are categorized by permanent or transient obstruction of blood flow, which impedes delivery of oxygen and essential nutrients to brain. In the last decade, the therapeutic window for tPA has increased from 3 to 5–6 h, and a new technique, involving the mechanical removal of the clot (endovascular thrombectomy) to allow reperfusion of the injured area, is being used more often. This last therapeutic approach can be done until 24 h after stroke onset. Due to this fact, more acute …

Self-Assembly Of 2d And 3d Metallo-Supramolecules With Increasing Complexity, Bo Song

USF Tampa Graduate Theses and Dissertations

Synthetic organic chemistry played a crucial role in the construction of molecules through the formation and dissociation of covalent bonds. However, the laborious synthetic procedures as well as the low yield after multiple steps have restricted the pursuit of complicated giant molecules with high efficiency. Being complementary to organic synthesis, self-assembly provided an alternative route to achieving the giant architectures using weak non-covalent interactions in high efficiency, which is in analog to natural systems such as DNA, peptide, and protein. Among the various interactions, coordination has shown unique advantages in terms of directionality, reversibility and strength. Serving as a bottom-up …

Design And Applications Of Charge-Separated Metal-Organic Frameworks, Sheela Thapa

Chemistry and Chemical Biology ETDs

Ionic tetrapodal ligands with colinear coordinating arms are very effective for designing hybrid porous materials with unusual structure and properties. The novelty of this research work lies in the utilization of a unique borate ligand that leads to charge-separated MOF structure with tailor designed properties. Borate ligands being tetrahedral afford 3D materials and the negative charge of borate anion can compensate the positive charge of metal ion in the framework. The borate ligands designed in this research consists of quaternary ammonium cation and anionic borate with four pyridine arms. These ligands upon coordination with Cu(I), Cu(II), Ag(I) and Co(II) metal …

The Potential Of Radium-224 As A Tracer Of Timescales Of Gulf Of Mexico Crude Oil Exposure To The Marine Environment, Matthew T. Kurpiel

Electronic Theses and Dissertations

Petroleum pollution in the marine environment can be deleterious to coastal and marine ecosystems and can have sustained effects for years. While oil slicks on the surface of the ocean are tracked with relative ease using satellite-based technology, deep sea, neutrally-buoyant hydrocarbon plumes remain exceedingly difficult to track. We provide evidence for the utility of Ra-224 as a potential hydrocarbon tracer to determine the marine exposure time of crude oil. We employed time course incubations to constrain a time dependent Ra-224 release signature and tested a variety of timescales, temporal resolutions, oil sources, seawater, and experimental treatments to determine potential …

Development Of Α-Aa Peptides As Peptidomimetics For Antimicrobial Therapeutics And The Discovery Of Nanostructures, Sylvia E. Singh

USF Tampa Graduate Theses and Dissertations

For decades it has been convention to use antibiotics for the treatment of bacterial infections. Due to the overuse and misuse of these drugs, bacteria are becoming resistant to these treatments. This phenomenon has led to the search for alternative antibiotics, and in the study of Host Defense Peptides (HDPs). HDPs are the body’s innate immune response to infection. They are known to modulate immune system response and kills bacterial using various methods causing them to be less susceptible to bacterial resistance. The method by which we can mimic these biological peptides is called peptidomimetics. Various research shows the use …

Electrification Ionization: Fundamentals And Applications, Bijay Kumar Banstola

LSU Doctoral Dissertations

Electrification ionization is a method to produce ions from solid samples by charge separation. This separation of charge can be enhanced by organic molecules known as matrix compounds to produce highly charged molecules. In this research, new methods were developed for the application of electrification ionization for surface analysis and the ionization mechanism was investigated. First, an electrification ionization matrix was used for tissue imaging using laser ablation. A two-component matrix of 2-nitrophloroglucinol and silica nanoparticles was found to increase the number of multiply charged ions from the tissue. Images of mouse brain with multiply charged ions were obtained. In …

The Chemical Ecology And Drug Discovery Potential Of The Antarctic Red Alga Plocamium Cartilagineum And The Antarctic Sponge Dendrilla Membranosa, Andrew Jason Shilling

USF Tampa Graduate Theses and Dissertations

Chemical ecology is the study of chemical interactions between organisms and their environment mediated by small molecules involved in nonessential physiological functions, known as secondary metabolites. These compounds can be crucial to survival of the organism, and have also provided the field of medicine with some of history’s most influential drugs, referred to in that context as natural products. Antarctica is a dynamic and understudied environment, which affords the opportunity to examine the chemical ecology of unique organisms while simultaneously evaluating their novel chemistry for potential therapeutic properties as natural products.

Plocamium cartilagineum is a red macroalgal species found in …

Aerial And Ground-Based Optical Gas Imaging Survey Of Uinta Basin Oil And Gas Wells, Seth N. Lyman, Trang Tran, Marc L. Mansfield, Arvind P. Ravikumar

Bingham Research Center

We deployed a helicopter with an infrared optical gas imaging camera to detect hydrocarbon emissions from 3,428 oil and gas facilities (including 3,225 producing oil and gas well pads) in Utah’s Uinta Basin during winter and spring 2018. We also surveyed 419 of the same well pads from the ground. Winter conditions led to poor contrast between emission plumes and the ground, leading to a detection limit for the aerial survey that was between two and six times worse than a previous summertime survey. Because the ground survey was able to use the camera’s high-sensitivity mode, the rate of detected …

Structures And Energetics Of Clusters Surrounding Diatomic Anions Stabilized By Hydrogen, Halogen, And Other Noncovalent Bonds, Steve Scheiner, Mariusz Michalczyk, Rafal Wysokiński, Wiktor Zierkiewicz

Chemistry and Biochemistry Faculty Publications

Diatomic anions CN-, NO-, and OH- are surrounded by 2, 3, and 4 ligand molecules drawn from the HF, HCl, XF, YF2, ZF3, TF4, and TrF3 set wherein X= Cl,Br, Y=S,Se, Z=P,As, T=Si,Ge, and Tr=Al,Ga. In the case of two ligands, both interact with the N of NO- and the O of OH-, but one approaches either end of CN-. Unlike the H and halogen bonding units, as the number of ligands increases there is a tendency for chalcogen, pnicogen, tetrel, and triel-bonding ligands to form a cage around the central anion, with strong inter-ligand noncovalent bonds. There are a …

Alignment Of Theoretically Grounded Constructs For The Measurement Of Science And Chemistry Identity, Kathryn Nicole Hosbein, Jack Barbera

Chemistry Faculty Publications and Presentations

Identity has been theorized to aid in student persistence within STEM disciplines. In this study, science and chemistry identity were defined as being recognized as a science or chemistry person within the classroom. To generalize the effects that identity has on student persistence, a measurable construct must be defined, operationalized, and tested in multiple settings with different populations. This project addressed the first step in the process, defining the construct and grounding it in an established theoretical framework. This qualitative project utilized a previously described physics identity framework, with sub-constructs of performance/competence, recognition, and interest, as a starting point for …

An Efficient Viologen-Based Electron Donor To Nitrogenase, Artavazd Badalyan, Zhi-Yong Yang, Bo Hu, Jian Luo, Maowei Hu, T. Leo Liu, Lance C. Seefeldt

Chemistry and Biochemistry Faculty Publications

Nitrogenase catalyzes the reduction of N₂ to NH₃, supporting all biological nitrogen fixation. Electron donors to this enzyme are ferredoxin or flavodoxin (in vivo) and sodium dithionite (in vitro). Features of these electron donors put a limit on spectrophotometric studies and electrocatalytic applications of nitrogenase. Although it is common to use methyl viologen as an electron donor for many low-potential oxidoreductases, decreased nitrogenase activity is observed with an increasing concentration of methyl viologen, limiting its utility under many circumstances. In this work, we suggest that this concentration-dependent decrease in activity can be explained …

The Total Syntheses Of Jbir-94 And Two Synthetic Analogs And Their Cytotoxicities Against A549 (Ccl-185) Human Small Lung Cancer Cells, Cathy L. Mangum, Mica B. Munford, Alyssa Sam, Sandra K. Young, Jeremy T. Beales, Yagya Prasad Subedi, Chad D. Mangum, Tanner J. Allen, Miranda S. Liddell, Andrew I. Merrell, Diana I. Saavedra, Becky L. Williams, Nicole Evans, Joseph L. Beales, Mike A. Christiansen

Chemistry and Biochemistry Faculty Publications

We here disclose the total syntheses of the natural polyphenol JBIR-94 and two nonnatural analogs, whose structures are of interest for their bioactivity potential as radical scavengers. Although we initially attempted this by dually acylating both of putrecine’s amine nitrogens in a single pot, our endeavors with this method (which has been successfully reported by other groups) proved ineffectual. We accordingly opted for the lengthier approach of acylating each amine individually, which gratuitously prevailed and also aligns with separate literature precedent. Moreover, we here share our analysis of these target compounds’ cytotoxicities and IC₅₀ values against A549 (CCL-185) human …

Detection Of Chalk In Single Kernels Of Long-Grain Milled Rice Using Imaging And Visible/Near-Infrared Instruments, Christopher K. Addison

Faculty Publications

Background and objectives To maintain the competitiveness of U.S. long-grain rice in U.S. and foreign markets, having translucent whole milled grain is critical. An objective technique to detect grain chalk, opaque areas in the grain, will provide breeders and industry with an effective tool for developing low-chalk varieties or agronomic practices that reduce chalk occurrence. Two instruments developed at the Center for Grain and Animal Health Research, U.S. Department of Agriculture-Agricultural Research Service (USDA-ARS), a single-kernel near-infrared (SKNIR) tube instrument and a silicon-based light-emitting diode (SiLED) high-speed sorter, were compared with two commercially available imaging instruments, WinSEEDLE and SeedCount used …

Emergent Functional Behaviour Of Humic Substances Perceived As Complex Labile Aggregates Of Small Organic Molecules And Oligomers, Robert L. Cook

Faculty Publications

The structural organisation of humic substances (HS) has been a central question of earth sciences for several decades. The latest experimental results have led to the recognition of HS as complex mixtures of small molecules and oligomers. We investigate the correlation between the chemical composition of HS, perceived as labile aggregates, and the emergent functions. Computational modelling was used to help to understand the processes and mechanisms on the molecular scale that occur in different fractions of the HS, fulvic acids (FA) and humic acids (HA), as they interact with metal ions and organic pollutants. The importance of non-covalent interactions …

How Oxygen Availability Affects The Antimicrobial Efficacy Of Host Defense Peptides: Lessons Learned From Studying The Copper-Binding Peptides Piscidins 1 And 3, Adenrele Oludiran, David S. Courson, Malia D. Stuart, Anwar R. Radwan, John C. Putsma, Myriam L. Cotten, Erin B. Purcell

Chemistry & Biochemistry Faculty Publications

The development of new therapeutic options against Clostridioides difficile (C. difficile) infection is a critical public health concern, as the causative bacterium is highly resistant to multiple classes of antibiotics. Antimicrobial host-defense peptides (HDPs) are highly effective at simultaneously modulating the immune system function and directly killing bacteria through membrane disruption and oxidative damage. The copper-binding HDPs piscidin 1 and piscidin 3 have previously shown potent antimicrobial activity against a number of Gram-negative and Gram-positive bacterial species but have never been investigated in an anaerobic environment. Synergy between piscidins and metal ions increases bacterial killing aerobically. Here, we …

Optimization Of Electrospray Ionization For Liquid Chromatography Time-Of-Flight Mass Spectrometry Analysis Of Preservatives In Wood Leachate Matrix, Kukowski Klara, Gysbers Brianna, Stephen Fisher, Alena Kubatova

Chemistry Faculty Publications

Triazoles and 3-iodo-2-propynyl butylcarbamate (IPBC) are commonly used wood preservatives active against a wide range of fungi and bacteria. As they are prone to leaching, their amounts need to be monitored by the industry to determine preservative loss from the products and for environmental impact assessment. Therefore, a liquid chromatography–electrospray–time-of-flight mass spectrometry (LC–ESI–TOFMS) method was developed and optimized for simultaneous quantification of triazoles and IPBC in aqueous wood extracts, specifically wood leachate. Analyte pre-concentration on a solid-phase extraction cartridge prior to the analysis yielded > 94% recoveries. ESI method parameters (e.g., solvent system, electrolyte type, electrolyte concentration, capillary and fragmentor voltages) …

Development Of Novel Peroxidase-Tio2/Zno Hybrid Catalysts For The Degradation Of Emerging Pollutants, Rana Fawzi Mohamed

Theses

Water pollution by different organic compounds is one of the most important environmental issues that is attracting the attention of many scientists due to its direct potential bad effect on human health. These organic pollutants include pesticides, pharmaceuticals, industrial wastes, and personal care products that are released in water bodies from domestic and industrial discharge. Various chemical, physical and biological approaches have been proposed to degrade these contaminants from the polluted water. In the present study, we immobilized versatile thermostable enzymes, Soybean peroxidase (SBP) and Horseradish peroxidase on functionalized photocatalysts—TiO₂ and ZnO to create novel bio-composite catalysts (SBP-TiO₂, SBP-ZnO, HRP-TiO₂, …

Alginate/Cucurbit [7] Uril/Dequalinium–Basedb Supramolecular Carbohydrates: Modulation Of Fret Signal By Temperature Control, Amir Alam Sohail

Chemistry Theses

Herein, we describe the synthesis of a bioactive, inexpensive, and easy-tohandle supramolecular carbohydrate polymer by grafting of cucurbit [7] uril macrocycle (CB7)-encapsulated dequalinium chloride hydrate (DCH) onto alginic acid carbohydrates (ALG) via amide linkage formation and show that light energy transfer based on energy migration can be controlled by altering polymer temperature without changing polymer composition. DCH (donor) and 2-anilinonaphthalene-6- sulfonic acid (acceptor) were used to generate Förster resonance energy transfer (FRET) signals. Stationary and time-resolved photoluminescence spectra of the modified carbohydrate platform revealed that FRET resulted in a color change from violet (~387 nm) to blue (~429 nm), which …

Hierarchical Nanostructuring Of Porous Silicon With Electrochemical And Regenerative Electroless Etching, Ermei Mäkilä, Anne-Mari Anton Willmore, Haibo Yu, Marianna Irri, Mark Aindow, Tambet Teesalu, Leigh Trevor Canham, Kurt W. Kolasinski, Jarno Salonen

Chemistry Faculty Publications

Hierarchically nanostructured silicon was produced by regenerative electroless etching (ReEtching) of Si powder made from pulverized anodized porous silicon. This material is characterized by ∼15 nm mesopores, into the walls of which tortuous 2–4 nm pores have been introduced. The walls are sufficiently narrow that they support quantum-confined crystallites that are photoluminescent. With suitable parameters, the ReEtching process also provides control over the emission color of the photoluminescence. Ball milling and hydrosilylation of this powder with undecylenic acid produces nanoparticles with hydrodynamic diameter of ∼220 nm that exhibit robust and bright luminescence that can be excited with either one ultraviolet/visible …

Thermo-Oxidative Degradation Of Hdpe Geomembranes: Effect Of Phenolic Antioxidant And Hindered Amine Light Stabilizer Concentrations, Yasin Kocak

USF Tampa Graduate Theses and Dissertations

High density polyethylene (HDPE) geomembrane is most common geomembrane which is mainly used for civil engineering applications. However, HDPE geomembrane loses its properties under oxidative degradation progress. This study aims to assess geomembranes which have different percentage of phenolic antioxidant and hindered amine light stabilizer (HALS) with under the six months of the thermal-oxidative degradation. The interactions between phenolic antioxidant, HALS and carbon black can affect the mechanical, physical and chemical properties. To monitor these properties, Differential Scanning Calorimetry (DSC), Fourier-transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM/EDX), Melt Index tests, …

Evaluating The Evidence Base For Evidence-Based Instructional Practices In Chemistry Through Meta-Analysis, Md Tawabur Rahman

USF Tampa Graduate Theses and Dissertations

Investigating the effectiveness of instructional practices provides an evidence base to inform instructional decisions. Synthesizing research studies on instructional effectiveness provides an estimate of the generalizability of effectiveness across settings, along with an exploration of factors that may moderate the impact, which cannot be achieved within individual studies. This study sought to provide a synthesis of evidence- based instructional practices (EBIPs) particular to chemistry through meta-analysis. 99 studies were analyzed comprising a broader view of chemistry specific studies than past meta-analyses. The results showed that EBIPs feature a demonstrably positive impact on students’ academic performance in chemistry, although assessment topic …

Near Real-Time Determination Of The Prevalence Of Cannabinoids, Cathinones, And Synthetic Opioids, Catherine O'Rourke, Bikram Subedi

Scholars Week

Unregulated new psychoactive substances (NPS) in “pure” or “preparation” forms are designed to mimic the effects of controlled substances, and are introduced and reintroduced in the market as a cheap substitute of established regulated drugs in quick succession to loophole the law enforcement efforts on combating drugs. For example, carfentanil, a synthetic opioid activates the opioid receptors similar to morphine but it is astoundingly potent compared to a typical drug of abuse (100 times more potent than fentanyl and 10,000 times more powerful than morphine). Based on the cost- and time-intensive forensic analysis, National Drug Early Warning System reported the …

Preparations And Electrochemical Properties Of Co@Nc Nanocomposites Based On Zif-67, Xiao-Li Tan, Deng-Hong He, Xing-Wang Zhang

Journal of Electrochemistry

It is necessary to develop an inexpensive catalyst for the replacement of precious metal catalysts (such as RuO₂, IrO₂). In this article, the metal organic framework ZIF-67 was synthesized by solvothermal method at room temperature, and then the high temperature carbonization was used to prepare the nitrogen-doped carbon-based composite material Co@NC with the Co nanoparticle inside. The effects of the carbonization temperature on surface morphology, chemcial composition and electrocatalytic property were investigated. Most importantly, the Co@NC catalyst with the best morphology and structure was synthesized, and its catalytic activity and stability toward oxygen evolution reaction (OER) …

Fate Of The Organophosphate Insecticide, Chlorpyrifos, In Leaves, Soil, And Air Following Application, Supta Das, Kimberly J. Hageman, Madeleine Taylor, Sue Michelsen-Heath, Ian Stewart

Chemistry and Biochemistry Faculty Publications

A field study was conducted to further our understanding about the fate and transport of the organophosphate insecticide, chlorpyrifos, and its degradation product, chlorpyrifos oxon. Leaf, soil and air sampling was conducted for 21 days after chlorpyrifos application to a field of purple tansy (Phacelia tanacetifolia). Air samples were collected using a high-volume air sampler (HVAS) and seven battery-operated medium-volume active air samplers placed around the field and on a 500-m transect extending away from the field. Chlorpyrifos was detected every day of the sampling period in all matrices, with concentrations decreasing rapidly after application. Chlorpyrifos oxon was …

Cross-Linked Poly(4-Vinylpyridine-N-Oxide) As A Polymer-Supported Oxygen Atom Transfer Reagent, Anna M. Bauer, Erin E. Ramey, Kjersti G. Oberle, Gretchen A. Fata, Chloe D. Hutchison, Christopher R. Turlington

Faculty Publications

Oxygen atom transfer (OAT) reagents are common in biological and industrial oxidation reactions. While many heterogeneous catalysts have been utilized in OAT reactions, heterogeneous OAT reagents have not been explored. Here, cross-linked poly(4-vinylpyridine-N-oxide), called x-PVP-N-oxide, was tested as a heterogeneous OAT reagent and its oxidation chemistry compared to its molecular counterpart, pyridine-N-oxide. The insoluble oxidant x-PVP-N-oxide demonstrated comparable reactivity to pyridine-N-oxide in direct oxidation reactions of phosphines and phosphites in acetonitrile, but x-PVP-N-oxide did not react in other solvents. The polymer backbone of x-PVP-N-oxide, however, allowed …

Chemical Synthesis Of Oligosaccharides From Human Milk, Mithila Dulanjalee Bandara Weerasooriya Mudiyanselage

Dissertations

Human milk oligosaccharides (HMO) are a family of structurally related glycans that are highly abundant in breast milk. Oligosaccharide fraction is the third largest solid component in human milk after lactose and lipids. There is an accumulating evidence that HMO can provide significant benefits to the breast-fed infants. However, understanding of the exact HMO functions is still incomplete due to the lack of individual compounds in sufficient quantities. Therefore, development of expeditious strategies for the chemical synthesis of HMO has been increasingly important. Among all the methods available for oligosaccharide synthesis, armed-disarmed strategy introduced by Fraser-Reid is based on chemoselective …

Quartz Crystal Microbalance Based Sensors For Detection And Discrimination Of Volatile Organic Compounds Using Ionic Materials, Stephanie R. Vaughan

LSU Doctoral Dissertations

Volatile organic compounds (VOCs) are prevalent in everyday life, ranging from household chemicals, naturally occurring scents from common plants and animals, to industrial-scale chemicals. Many of these VOCs are known to cause adverse health and environmental effects and require regulation to prevent pollution. Detecting VOCs plays a critical role in food quality control, environmental quality control, medical diagnostics, and explosives detection. Thus, development of adequate sensing devices for detection and discrimination of VOCs is of great importance. In recent years, use of quartz crystal microbalance (QCM) based sensor arrays for analyses of VOCs has attracted significant interest. Detection of VOCs …