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The Detection And Quantitative Analysis Of Endocannabinoids And Endogenous Fatty Acid Amides In Apis Mellifera And Tribolium Castaneum, Perry Robert Mitchell Jr.

USF Tampa Graduate Theses and Dissertations

Endocannabinoids, and the fatty acid amides from which they are a member, have garnered greater scientific interest in the last two decades due to the cannabimimetic properties of these endogenous molecules. The most well-known of these is Anandamide, which has thus far been discovered in several species of animal ranging from C. elegans, fruit flies, to bovine and humans. Because of the importance and increasing impact of these compounds a brief overview is first presented herein, with a major focus on the N-acyldopamines due to the direct impact they potentially pose to human physiology.

Secondly, the detection and …

Autophagy-Mediated Mechanisms Of Chemoresistance In Cancer, David Broadbent, Dr. Joshua Andersen

Journal of Undergraduate Research

The resistance of tumor cells to chemotherapy is a critical problem in the clinic and is a common cause of mortality in cancer. Emerging data suggests that resistance to chemotherapy is caused by a tumor-expressed protein called 14-3-3ζ, yet the mechanism to explain 14-3-3ζ-mediated chemoresistance is not completely understood (1). Rapid growing tumors often outgrow their blood supply resulting in regions of hypoxia (low glucose and oxygen). These cells must adapt or die and those that do adapt often become metastatic and chemoresistant. A recently proposed mechanism by which cancer cells are able to adapt to hypoxia is via autophagy, …

Comparative Genomics Of Cluster O Mycobacteriophages, Steven G. Cresawn, Welkin H. Pope, Deborah Jacobs-Sera, Charles A. Bowman, Daniel A. Russell, Rebekah M. Dedrick, Tamarah Adair, Kirk R. Anders, Sarah Ball, David Bollivar, Caroline Breitenberger, Sandra H. Burnett, Kristen Butela, Deanna Byrnes, Sarah Carzo, Dr. Kathleen Cornely, Trevor Cross, Richard L. Daniels, David Dunbar, Ann M. Findley, Chris R. Gissendanner, Urszula P. Golebiewska, Grant A. Hartzog, J. Robert Hatherill, Lee E. Hughes, Chernoh S. Jalloh, Carla De Los Santos, Kevin Ekanem, Sphindile L. Khambule, Rodney A. King, Christina King-Smith, Karen Klyczek, Greg P. Krukonis, Christian Laing, Jonathan S. Lapin, A. Javier Lopez, Sipho M. Mkhwanazi, Sally D. Molloy, Deborah Moran, Vanisha Munsamy, Eddie Pacey, Ruth Plymale, Marianne Poxleitner, Nathan Reyna, Joel F. Schildbach, Joseph Stukey, Sarah E. Taylor, Vassie C. Ware, Amanda L. Wellmann, Daniel Westholm, Donna Wodarski, Michelle Zajko, Thabiso S. Zikalala, Roger W. Hendrix, Graham F. Hatfull

Chemistry & Biochemistry Faculty Publications

Mycobacteriophages – viruses of mycobacterial hosts – are genetically diverse but morphologically are all classified in the Caudovirales with double-stranded DNA and tails. We describe here a group of five closely related mycobacteriophages – Corndog, Catdawg, Dylan, Firecracker, and YungJamal – designated as Cluster O with long flexible tails but with unusual prolate capsids. Proteomic analysis of phage Corndog particles, Catdawg particles, and Corndog-infected cells confirms expression of half of the predicted gene products and indicates a non-canonical mechanism for translation of the Corndog tape measure protein. Bioinformatic analysis identifies 8–9 strongly predicted SigA promoters and all five Cluster O …

Purine-Based Triazoles, Prakash Reddy, Nanditha G. Nair, Mark A. Smith, Wataru Kudo

Chemistry Faculty Research & Creative Works

A pharmaceutical composition for inhibiting at least protein kinase in a cell of a subject includes a purine based triazole.

Ua66 Ogden College Of Science & Engineering Newsletter, Cheryl Stevens, Dean

Ogden College of Science & Engineering Publications

No abstract provided.

Synthesis Of 2-Acylphenol And Flavene Derivatives From The Ruthenium-Catalyzed Oxidative C-H Acylation Of Phenols With Aldehydes, Hanbin Lee, Chae S. Yi

Chemistry Faculty Research and Publications

The cationic ruthenium hydride complex [(C₆H₆)(PCy₃)(CO)RuH]⁺BF₄⁻ has been found to be an effective catalyst for the oxidative C–H coupling reaction of phenols with aldehydes to give 2-acylphenol compounds. The coupling of phenols with α,β-unsaturated aldehydes selectively gives the flavene derivatives. The catalytic method mediates direct oxidative C–H coupling of phenol and aldehyde substrates without using any metal oxidants or forming wasteful byproducts.

Optimization Of Nonadsorptive Polymerized Polyethylene Glycol Diacrylate As A Material For Microfluidics And Sensor Integration, Chad Rogers

Theses and Dissertations

Microfluidics is a continually growing field covering a wide range of applications, such as cellular analysis, biomarker quantification, and drug discovery; but in spite of this, the field of microfluidics remains predominately academic. New materials are pivotal in providing tailored properties to improve device integration and decrease prototype turnaround times. In biosensing, nonspecific adsorption in microfluidic systems can deplete target molecules in solution and prevent analytes, especially those at low concentrations, from reaching the detector. Polyethylene glycol diacrylate (PEGDA) mixed with photoinitiator forms, on exposure to ultraviolet (UV) radiation, a polymer with inherent resistance to nonspecific adsorption. Optimization of the …

Electrochemical Monitoring Of Cell Wall-Regulated Transient Extracellular Oxidative Burst From Single Plant Cells, Jun-Tao Liu, Yan-Ling Liu, Zhi Cheng, Shi-Jing Chen, Wei-Hua Huang

Journal of Electrochemistry

Oxidative burst by rapid, transient generation of reactive oxygen species (ROS) is a fundamental process for plant disease defense and signal transduction. ROS can be protective or toxic depending on their concentrations, and critical balance between ROS production and scavenging is regulated by complex and perfect mechanisms in plant cells. However, the process of rapid and transient ROS burst from plant cells and their regulatory mechanisms are far from being completely understood, owing to the methodological obstacles in real-time monitoring such a fast process. In this work, we showed the application of microelectrode electrochemistry with high spatiotemporal resolution to monitor …

Novel Dna Electrochemical Biosensor For K-Ras Point Mutation Detection Based On Dna Polymerase I, Li-Qing Lin, Cheng-Fei Zhao, Zhou-Qian Jiang, Shao-Huang Weng, Xiao-Lan Xie, Xin-Hua Lin

Journal of Electrochemistry

In this article, we developed a novel DNA electrochemical sensor for obtaining a current-time curve based on DNA polymerase I. The capture probes were fixed on the Au electrode by Au interacting with -SH, and then hybridized with the K-ras mutant target DNA as far as one base before the mutation site. After hybridizing the K-ras mutant or wild target DNA, the resulting assembly reacted with the dUTP-biotin in the presence of DNA polymerase I. Then avidin-HRP combined the dUTP-biotin on the electrode. The proposed electrode was applied for detection in TMB solution by electrochemical technology. The experimental results showed …

A Multi-Channel Electrochemical Immunosensing System With Polyhrp-Based Signal Amplification For The Detection Of Tumor Markers, Wang-Ping Deng, Yan-Zhi Dou, Jing Su, Lin Hao, Shi-Ping Song, Chun-Hai Fan

Journal of Electrochemistry

We have developed a multi-channel electrochemical immunosensing system for the detection of α-fetoprotein (AFP). The sensing system consisted of carbon screen-printed electrode (SPCE) arrays and polyHRP-based signal amplification probes. AFP antigens could bind to both capture antibodies immobilized on electrode arrays ant detection antibodies (anti-AFP IgG developed in rabbit). The anti-rabbit IgG conjugated to poly-horseradish peroxidase were used as a signaling probe to bind to the immuno-complex. The current signals were harvested by a home-made multi-channels electrochemical detector. AFP could be detected in the concentration ranges of 64 pg·mL^-1 ~ 250 ng·mL^-1. The detection limit was as …

Fabrication And Application Of Cytochrome P450 Electrochemcial Biosensor In Drug Metabolism, Xuan Xu, Ju-Sheng Lu, Song-Qin Liu

Journal of Electrochemistry

The process of drug metabolism plays an important role in drug efficacy and toxicity in vivo. Thus, the development of cheap, continent, rapid and high-throughput method for drug metabolism studies has great guiding significance for the design of new drugs, the determination of drug dosage and the detection of clinical drugs. Since the key role played by Cytochrome P450 (CYP450) in phase-I drug reaction, the constructed CYP450 enzyme biosensor can be used for the initial screening of drugs. It is found that the replacement of coenzyme NADPH with an electrode is to provide two electrons demanded in the catalytic reaction. …

Preparation And Properties Of Titanium Based Metal Oxide Electrodes For Ammonia Nitrogen Wastewater Treatment, Xue Li, Meng Xue, Ling Huang, Jun-Tao Li, Shi-Gang Sun

Journal of Electrochemistry

In this paper, four types of titanium based metal oxides electrodes were prepared by thermal decomposition method: Ti/SnO₂+Sb₂O₃, Ti/SnO₂+Sb₂O₃/SnO₂+IrO₂, Ti/SnO₂+Sb₂O₃/SnO₂+RuO₂, Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂. The XRD results show that CeO₂ in Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂ displayed a good crystal structure, and there was no significant oxygen evolution reaction occurred after electrolytic oxidation. Compared with the other three electrodes, the Ce-doped …

Naio4 Oxidation Of Mussel Adhesive Protein Film And Its Corrosion Protection For Mg-1.0ca Alloy, Rui-Qing Hou, Ping-Li Jiang, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

The effect of oxidation of mussel adhesive protein (Mefp-1) film on the corrosive resistance for Mg-1.0Ca alloy was investigated by scanning electron microscopy (SEM), atom force microscopy (AFM), electron probe microanalysis (EPMA), Infrared reflection absorption spectroscopy (IRAS) and electrochemical methods. The results showed that the NaIO₄ induced oxidation of the pre-formed Mefp-1 film with porous morphology involved structural change of the DOPA group in the protein and resulted in a more uniform film with net-like morphology. The protein film without oxidation had an increasing resistance for the corrosion of Mg-1.0Ca alloy up to 7 days exposure. After oxidation, Epit …

"Probing The Transition State Region In Catalytic Co Oxidation On Ru" Data Files, H. Öström, H. Öberg, H. Xin, Jerry L. Larue, M. Beye, M. Dell'angela, J. Gladh, M. L. Ng, J. A. Sellberg, S. Kaya, G. Mercurio, D. Nordlund, W. F. Schlotter, A. Föhlisch, M. Wolf, W. Wurth, M. Persson, J. K. Nørskov, F. Abild-Pedersen, H. Ogasawara, L. G. M. Pettersson, A. Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Data Sets

Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on Ru initiated by an optical laser pulse. On a timescale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface allowing the reactants to collide and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond-formation between CO and O with a distribution of OC—O bond lengths close to the transition state (TS). After …

Probing The Transition State Region In Catalytic Co Oxidation On Ru, H. Öström, H. Öberg, H. Xin, Jerry L. Larue, M. Beye, M. Dell'angela, J. Gladh, M. L. Ng, J. A. Sellberg, S. Kaya, G. Mercurio, D. Nordlund, M. Hantschmann, F. Hieke, D. Kühn, W. F. Schlotter, G. L. Dakovski, J. J. Turner, M. P. Minitti, A. Mitra, S. P. Moeller, A. Föhlisch, M. Wolf, W. Wurth, M. Persson, J. K. Nørskov, F. Abild-Pedersen, H. Ogasawara, L. G. M. Pettersson, A. Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on Ru initiated by an optical laser pulse. On a timescale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface allowing the reactants to collide and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond-formation between CO and O with a distribution of OC—O bond lengths close to the transition state (TS). After …

The Infrared Spectrum Of The He-C2d2 Complex, N. Moazzen-Ahmadi, A. R. W. Mckellar, Berta Fernandez, David Farrelly

Chemistry and Biochemistry Faculty Publications

Spectra of the helium-acetylene complex are elusive because this weakly bound system lies close to the free rotor limit. Previously, limited assignments of He–C2D2 transitions in the R(0) region of the ν3 fundamental band (≈2440 cm⁻¹) were published. Here, new He–C2D2 infrared spectra of this band are obtained using a tunable optical parametric oscillator laser source to probe a pulsed supersonic slit jet expansion from a cooled nozzle, and the analysis is extended to the weaker and more difficult P(1) and R(1) regions. A term value approach is used to obtain a consistent set of “experimental” energy levels. …

Design, Synthesis And Applications Of Polymer Biomaterials, Frankie Costanza

USF Tampa Graduate Theses and Dissertations

The emergence of antibiotic resistant bacteria has prompted the research into novel kinds of antibacterial small molecules and polymers. Nature has solved this issue with the use of cationic antimicrobial peptides, which act as nonspecific antibiotics against invading species. Herein, we have tried to mimic this general mechanism in a biocompatible and biodegradable polymer micelle based on the polymerization of naturally occurring amino acids lysine and phenylalanine linked to a PEG tether. This amphiphilic structure allows for the spontaneous collapse into stable nanoparticles in solution, which contains a hydrophilic outer layer and a hydrophobic core. Our polymers have shown activity …

Identification And Quantification Of Gaseous Organic Compounds Emitted From Biomass Burning Using Two-Dimensional Gas Chromatography–Time-Of-Flight Mass Spectrometry, L. E. Hatch, W. Luo, J. F. Pankow, Robert Yokelson, C. Stockwell, K. C. Barsanti

Chemistry and Biochemistry Faculty Publications

The current understanding of secondary organic aerosol (SOA) formation within biomass burning (BB) plumes is limited by the incomplete identification and quantification of the non-methane organic compounds (NMOCs) emitted from such fires. Gaseous organic compounds were collected on sorbent cartridges during laboratory burns as part of the fourth Fire Lab at Missoula Experiment (FLAME-4) and analyzed by two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-ToFMS). The sensitivity and resolving power of GC x GC-ToFMS allowed the acquisition of the most extensive data set of BB NMOCs to date, with measurements from 708 positively or tentatively identified compounds. Estimated emission factors …

Sulfidic Spring In The Gypsum Karst System Of Monte Conca (Italy): Chemistry And Microbiological Evidences, Marianna Messina, Tiziana Grech, Fiorenzo Fiorenza, Alessandro Marlettta, Pietro Valenti, Salvatore Petralia

International Journal of Speleology

Monte Conca Cave is a karst system placed in Messinian evaporites, consisting of an active cave and a resurgence located on the massif of Monte Conca, Campofranco within the "Riserva Naturale Integrale di Monte Conca". A sulfidic spring is located in the terminal gallery of the cave. To characterize the physical and chemical parameters of the Monte Conca cave and of the sulfidic spring, air temperature, relative humidity, water pH, and concentrations of dissolved sulfides, nitrates and sulfates were monitored. The high sulfide consumption rate in the sulfidic spring, evaluated by a kinetic study, suggests that biotic consumption is dominant. …

The Exchanged Ef-Hands In Calmodulin And Troponin C Chimeras Impair The Ca2+-Induced Hydrophobicity And Alter The Interaction With Orai1: A Spectroscopic, Thermodynamic And Kinetic Study, Drake Jensen, Nicole Reynolds, Ya-Ping Yang, Shubha Shakya, Zhi-Qiang Wang, Dennis J. Stuehr, Chin-Chuan Wei

Chemistry Faculty Research, Scholarship, and Creative Activity

Background

Calmodulin (CaM) plays an important role in Ca²⁺-dependent signal transduction. Ca²⁺ binding to CaM triggers a conformational change, forming a hydrophobic patch that is important for target protein recognition. CaM regulates a Ca²⁺-dependent inactivation process in store-operated Ca²⁺entry, by interacting Orai1. To understand the relationship between Ca²⁺-induced hydrophobicity and CaM/Orai interaction, chimera proteins constructed by exchanging EF-hands of CaM with those of Troponin C (TnC) are used as an informative probe to better understand the functionality of each EF-hand.

Results

ANS was used to assess the context of the induced …

Gamma-Aapeptides As A New Class Of Peptidomimetics: Synthesis, Structures, And Functions, Haifan Wu

USF Tampa Graduate Theses and Dissertations

Peptidomimetics are synthetic oligomers that resemble the activities of peptides. Their advantages over peptides include high stability towards proteolysis and enormous chemical diversity. Over the past two decades, there have been extensive efforts to develop peptide mimics, such as beta-peptides, peptoids, D-peptides, etc. The research on peptidomimetics have led to many important applications in both medicinal and material science. In order to explore new functions, the discovery of peptidomimetics with novel frameworks is essential. We reported the synthesis and evaluation of a new class of peptidomimetics, termed as gamma-AApeptides. Previous studies of gamma-AApeptides have revealed that gamma-AApeptides are highly resistant …

Functional Expression And Characterization Of A Truncated Candida Antarctica Lipase B In Yeast, Samantha Robinson

Theses and Dissertations

Candida antarctica lipase B is an enzyme capable of hydrolyzing ester bonds in a lipid-water interface with potential to become a useful biocatalyst for production of biodiesel fuel. Enzymatically catalyzing the transesterification of triacylglycerides to produce fatty acid alkyl esters (biodiesel) is an environmentally cleaner alternative to the current process which utilizes chemical reagents as catalysts. Optimization and development of strains to express highly active, stable, large quantities of these biocatalysts is essential for inexpensive production of biodiesel. Additionally, lipase enzymes can be immobilized onto a resin, eliminating the need to recover the catalyst from the product and allowing multiple …

A Novel Chemosynthetic Peptide With Β-Sheet Motif Efficiently Kills Klebsiella Pnuemoniae In A Mouse Model, Shirui Tan, Changpei Gan, Rongpeng Li, Yan Ye, Shuang Zhang, Xu Wu, Yi Yan Yang, Weimin Fan, Min Wu

Chemistry Faculty Publications

Klebsiella pneumoniae (Kp) is one of the most common pathogens in nosocomial infections and is increasingly becoming multiple drug resistant. However, the molecular pathogenesis of Kp in causing tissue injury and dysregulated host defense remains elusive, further dampening the development of novel therapeutic measures. We have previously screened a series of synthetic antimicrobial beta-sheet forming peptides and identified a peptide (IRIKIRIK; ie, IK8L) with a broad range of bactericidal activity and low cytotoxicity in vitro. Here, employing an animal model, we investigated the antibacterial effects of IK8L in acute infection and demonstrated that peritoneal injection of IK8L to mice down-regulated …

The Stoichiometry Of Metal Assisted Etching (Mae) Of Si In V2o5 + Hf And Hooh + Hf Solutions, Kurt W. Kolasinski, William B. Barclay, Yu Sun, Mark Aindow

Chemistry Faculty Publications

No abstract provided.

Design And Synthesis Of Bioactive Peptidomimetics, Yaogang Hu

USF Tampa Graduate Theses and Dissertations

Protein-Protein Interactions (PPIs) play a very important role in biological functions and therefore the inhibition of specific Protein-Protein Interactions has a huge therapeutic value. The most successful small molecular PPIs inhibitors do not fit with the prevalent `Rule of Five' drug profile. To overcome the disadvantages of small molecular PPIs inhibitors, peptide based PPIs inhibitors were developed. Herein we describe the development of a new class of peptidomimetics AA-peptides. The AApeptides were designed based on chiral PNA backbone. Substitution of nucleobases yields AApeptides that are resistant to proteolysis and capable of mimicking peptides. Two types of AApeptides were discussed in …

Optimization Of Aggregating Agents And Sers Substrates For Sers Detection Of Cotinine And Trans 3'-Hydroxycotinine, Sungyub Han

USF Tampa Graduate Theses and Dissertations

This dissertation mainly focuses on applications of Surface Enhance Raman Scattering (SERS) to detect tobacco-related biomarkers with optimized experimental conditions (pH and aggregating agents) and SERS substrates (silica core and silver shell nanoparticles). Cotinine (COT) and trans 3-hydroxycotinine (3HC), metabolized from nicotine as one of main chemicals of tobacco, have been used as tobacco biomarkers because their half-life are longer than that of nicotine, which enable to monitor the tobacco exposure. The effects of aggregating agents and pH on SERS detection of COT and 3HC were investigated. Aggregating agents play an important role in SERS detection of target molecules since …

Intramolecular S···O Chalcogen Bond As Stabilizing Factor In Geometry Of Substituted Phenyl-Sf3 Molecules, Vincent De Paul Nziko, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Density functional methods are used to examine the geometries and energetics of molecules containing a phenyl ring joined to the trigonal bipyramidal SF3 framework. The phenyl ring has a strong preference for an equatorial position. This preference remains when one or two ether -CH2OCH3 groups are added to the phenyl ring, ortho to SF3, wherein an apical structure lies nearly 30 kcal/mol higher in energy. Whether equatorial or apical, the molecule is stabilized by a S···O chalcogen bond, sometimes augmented by CH···F or CH···O H-bonds. The strength of the intramolecular S···O bond is estimated to lie in the range between …

Towards The Total Synthesis Of (+/-)-Gephyrotoxin 287c, Maciej E. Domaradzki

Dissertations, Theses, and Capstone Projects

Studies directed toward the total synthesis of (+/-)-Gephyrotoxin 287C are described herein. Even though the target alkaloid has been synthesized four times to date, it still presents an interesting synthetic challenge. Our ultimate goal is to develop an efficient enantioselective synthetic route utilizing oxazolone chemistry in order to demonstrate its utility as a dienophilic component in intramolecular Diels-Alder reactions. This is part of a greater ongoing study aimed at a range of suitable alkaloid targets.

Chapter 1 provides introduction to frog toxins as secondary metabolites and subsequently shifts to the target alkaloid. (+/-)-Gephyrotoxin 287C was originally described by Daly and …

State-To-State Reaction Dynamics Of ¹⁸O+³²O₂ Studied By A Time-Dependent Quantum Wavepacket Method, Wenbo Xie, Lan Liu, Zhigang Sun, Hua Guo, Richard Dawes

Chemistry Faculty Research & Creative Works

The title isotope exchange reaction was studied by converged time-dependent wave packet calculations, where an efficient 4th order split operator was applied to propagate the initial wave packet. State-to-state differential and integral cross sections up to the collision energy of 0.35 eV were obtained with ³²O₂ in the hypothetical j₀ = 0 state. It is discovered that the differential cross sections are largely forward biased in the studied collision energy range, due to the fact that there is a considerable part of the reaction occurring with large impact parameter and short lifetime relative to the rotational period …

Highly-Selective Chemiresistive Sensing And Analysis Of Vapors Using Functionalized Nanotubes, Deon Hines

Dissertations, Theses, and Capstone Projects

Specifically, the project involves the development of a diversified array of nanostructured gas-sensors comprised of selectively, novel surface-functionalized carbon nanotubes (for analyte selectivity by virtue of functionality). Harnessing carbon nanotubes with various electron withdrawing and donating groups help in determining their affinity toward certain prognostic gaseous markers thus increasing specificity of such created sensors. We have devised synthetic routes that have led to the facile production of covalently polyfunctionalized nanotubes in high yield. Seven carbon nanotube analogues were systematically considered and then chemically synthesized, from pristine single-walled nanotubes (SWNT's), for use as the main component of sensory units that was …