Digital Commons Network^™

Changes In Apparent Molar Water Volume And Dkp Solubility Yield Insights On The Hofmeister Effect, Daryl K. Eggers, A. Y. Payumo, R. M. Huijon, D. D. Mansfield, L. M. Belk, A. K. Bui, A. E. Knight

Faculty Publications, Chemistry

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the nonideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the …

Development, Validation And Application Of Uhplc-Ms/Ms Methods For The Detection Of Veterinary Drug Residues In Food Of Animal Origin, Michelle Whelan

Theses

Ultra high pressure liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-MS/MS) technology was utilized for the development of analytical methods for the detection of veterinary drug residues in foods of animal origin. Initial work focused on the development of the mass spectrometry (MS) method for the detection of the analytes of interest and subsequent chromatographic separation. The MS method was optimised to detect both positively and negatively ionised analytes from different classes in a single injection in a 13 minute run time at μg kg^-1levels.

Sample preparation procedures were modified to extract the residues from muscle and …

Diffusion And Random Walks, Lewis Ludwig, Annabel Edwards

Faculty Publications

No abstract provided.

The Synthesis, Characterization, And Upconverting Properties Of Erbium Doped; Ytterbium, Erbium Co-Doped Yttrium Oxysulfide Phosphors Under 808, 980, And 1560 Nm Excitation, James Wilkins

Theses and Dissertations

Bulk yttrium oxysulfide phosphors were prepared using the polysulfide flux method. The morphology and structure was characterized using transmission electron microscopy and x-ray powdered diffraction. Visible emissions occurring near 530 and 550 nm and 660 - 670 nm consistent with the 2H11/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions, respectively, were observed under 808, 980, and 1560 nm excitation. The upconverting mechanisms excited at 808, 980, and 1560 nm have been investigated in detail. The power dependent behavior of the upconverted emission intensities for singly doped erbium phosphors excited at 808 and 980 nm indicated a two-photon excitation process. …

Synthesis Of Small Molecule Inhibitors Of Janus Kinase 2, Phosphodiesterase Iv, Gabaa And Nmda Receptors: Investigation Of Mcmurry, Mannich And Chemoenzymatic Strategies, Meghanath Gali

USF Tampa Graduate Theses and Dissertations

Stilbenoids possess a wide range of biological properties such as, anticancer, antiplatelet aggregation, antiestrogenic, antibacterial, antifungal and antiatherogenic, etc. Owing to these therapeutic values, a great deal of attention attracted in the synthesis of derivatives of stilbenes. During the course of the study, G6 a novel stilbenoid was discovered, through high throughput screening, to be a potent inhibitor of mutated JAK2-V617F. The mutated JAK2 variant has been implicated in various myeloproliferative disorders (MPDs) including polycythemia vera (PV), essential thrombocythemia (ET) and primary myelofibrosis (PMF) has been targeted by therapeutics. Chapter 2 describes the synthesis of analogs of the stilbenoid G6 …

Natural Product Drug Discovery Against Tropical Diseases, Wai Sheung Ma

USF Tampa Graduate Theses and Dissertations

This dissertation describes the isolation of secondary metabolites from natural origins through a series of chromatographic techniques and spectrometric characterization in the effort of drug discovery. The isolated compounds obtained were used as drug leads against tropical diseases, namely malaria and leishmaniasis. While first chapter offers an introduction on the use of a natural product by itself as an effective therapeutic and its role on inspiring the discovery of new drugs, the later chapters will concentrate on isolation and characterization of bioactive natural products from an Antarctic sponge and mangrove endophytic fungi during the dissertation work.

The second chapter describes …

Chemical Investigation Of The Antarctic Marine Invertebrates Austrodoris Kerguelenensis & Dendrilla Membranosa And The Antarctic Red Alga Gigartina Skottsbergii, John Alan Maschek

USF Tampa Graduate Theses and Dissertations

The marine realm and, in particular, the Antarctic benthos is largely unexplored and understudied. The chemical investigation reported herein reveals not only the biodiversity, but how that biodiversity manifests remarkable chemical diversity. In our continuing study of the nudibranch Austrodoris kerguelenensis, we have isolated a diverse suite of diterpenoid glyceride esters, palmadorins D - S (2.32 - 2.47), one of which is the first reported halogenated diterpene from a dorid nudibranch. Utilizing genomic data from collaborators, we have investigated the chemical diversity from phylogenetically unique specimens collected in close proximity to one another. Chemical groupings based on comparison of LC/MS …

Crystal Engineering Of Pharmaceutical Cocrystals, Sreya Mukherjee

USF Tampa Graduate Theses and Dissertations

Pharmaceutical cocrystals use principles of crystal engineering for the design of crystalline forms of drugs and can improve their solubility, bioavailability, stability and other important properties without changing the efficacy of the drug. Herein reported are pharmaceutical cocrystals of two API's, caffeine and Pentoxifylline.

Research has indicated that caffeine has the ability to reverse AB; plaque deposition in the brain (believed to be the primary cause of Alzheimer's pathogenesis) and thus revert memory and improve cognitive impairment. But owing to the fast absorption rate and short half life, a controlled release formulation of caffeine would be clinically beneficial. Thus, novel …

Sol-Gel Resorcinarene Sorbent For Capillary Microextraction Coupled To Gas Chromatography, Abdullah Awadh Alhendal

USF Tampa Graduate Theses and Dissertations

For the first time, octahydroxyl methylresorcinarene with four hexyl groups on the lower rim was utilized in the in-situ preparation of a silica-based sol-gel organicinorganic hybrid coating for sample preconcentration by capillary microextraction (CME). Tetraethoxysilane (TEOS) was chosen as a sol-gel precursor to create a crosslinked sol-gel network via acid-catalyzed hydrolytic polycondensation reactions. Sol-gel chemistry helped in the in situ preparation of resorcinarene-containing extraction phase in the form of a surface coating. It also provided an effective means to chemically bind the coating to the inner surface of fused silica capillary via condensation of the hydroxyl groups in the sol-gel …

Synthesis And Characterization Of Self-Healing Poly (Carbonate Urethane) Carbon-Nanotube Composites, Roger Wesley Bass

USF Tampa Graduate Theses and Dissertations

Synthesis of high molar mass polycarbonate polyurethanes using a novel polyol is described. The resulting elastomers demonstrate excellent mechanical properties as well as the capability to re-heal after rupture without the addition of additives or imbedded healing agents. The self-healing functionality is shown to greatly improve with the addition of up to 1% single and multi-walled carbon nanotubes. The interface of the carbon nanotubes and self-healing polymer are probed using Raman techniques and provide an insight into how the self-healing actions are improved with the addition of carbon nanotubes.

Synthesis of polycarbonate polyurethanes and carbon nanotube composites using a novel …

Lead Discovery And Optimization Strategies Towards The Development Of 4(1h)-Quinolones And 1,2,3,4-Tetrahydroacridone Analogs With Antimalarial Activity, Richard Matthew Cross

USF Tampa Graduate Theses and Dissertations

The goal of our research endeavor was to successfully employ modern lead discovery and optimization strategies towards the development and identification of compounds possessing antimalarial activity. Preliminary data from in vitro screening at the Walter Reed Army Institute of Research identified several chemotypes including 4(1H)-quinolones and 1,2,3,4-tetrahydroacridones to have potent antimalarial activities. Multiple synthetic routes were devised and implemented which enabled the rapid preparation and isolation of over 400 structurally diverse 4(1H)-quinolones and 1,2,3,4-tetrahydroacridones.

Our research towards discovering and optimizing antimalarials was inspired from the severe impact malaria has had on our planet especially on impoverished countries. There are over …

Guanidines, Amidines And Carbamides As Novel Sigma Receptor Ligands For Post-Stroke Therapeutics, Michelle Yolanda Cortes-Salva

USF Tampa Graduate Theses and Dissertations

Stroke is the 3^rd leading cause of death in the United States. For this reason, it has become our goal to find a drug that is capable of reestablishing intracellular and extracellular Ca⁺² flux upon direct binding to the sigma receptor, which can be delivered easily and efficiently. Our active research focuses the development of guanidine analogues that can serve as therapeutic drugs which target sigma 1 and sigma 2 receptors having a direct effect on Ca⁺² levels on the cell. The use of symmetrical guanidine analogues such as N,N'-di-o-tolyl guanidine (o-DTG) as therapeutic drugs for ischemic …

Synthesis And Antimicrobial Activities Of S,S'-Heterosubstituted Disulfides, Praveen Ramaraju

USF Tampa Graduate Theses and Dissertations

Antibiotic resistance is a particularly critical health concern and has increased dramatically over the past two decades. For over a decade the Turos laboratory has been designing small molecules to target pathogenic microbes such as Staphylococcus aureus and the resistant variants like methicillin-resistant Staphylococcus aureus (MRSA). Previously, N-thiolated Β-lactams, N-thiolated 2-oxazolidinones and aromatic disulfides that were synthesized in Dr. Turos' lab have shown strong activity against these bacteria. The present work describes the synthesis and antimicrobial activities of a related structural class called S,S'-heterosubstituted disulfides. For ages, sulfur (elemental) has been used as an antibacterial for controlling infestation and bacterial …

Synthesis And Binding Studies Of Peptide Mimetics, Anion Receptors, And Kinase Inhibitors, Nanditha G. Nair

Doctoral Dissertations

"A series of novel purine-based fluoroaryl triazoles were synthesized and assayed for their neuroprotective effects of hippocampal slice culture exposed to amyloid beta (Aß) oligomers. A monofluorinated triazole has been identified which has comparable neuroprotective effect as that of flavopiridol and roscovitine against the Aß induced neurotoxicity. Carnosine and histidine are biologically interesting antioxidants. In order to probe whether they exert their antioxidant effect through metal ion chelation, the Cu(ll) ion chelating abilities of these compounds were measured by UV-vis spectroscopy. Amyloid beta, the major component of senile plaques in Alzheimer's disease, is known to complex transition metal ions through …

Part-I Characterization Of Phorbol Ester; The Predominant Toxic Component Of Jathropha Curcas And Development Of An Efficient Process For The Detoxification Of Jathropha Curcas Meal Part-Ii Quantification Of 2-Hydroxy-4-(Methylthio) Butanoic Acid And Pantothenic Acid In Bovine Serum And Sea Water Matrices, Balaji Viswanathan

Doctoral Dissertations

"Jatropha curcas is has often been touted as the most sustainable biofuel source. Jatropha curcas is a drought resistant perennial plant belonging to the Euphorbiaceae family. Interest in this plant as a biofuel source is related to high lipid (triglyceride) content of its seeds. However, economics of jatropha as a biofuel source has been marred by the toxicity of the oil and its protein rich meal. As a result of high toxicity the protein rich meal is used only as a very low or no economic value organic fertilizer. Economic return from jatropha can be dramatically enhanced through development of …

Optimization And Validation Of Direct Analysis In Real Time Mass Spectrometry (Dart-Ms) For Quantitation Of Sugars To Advance Biofuel Production, Daudi Sayialel Saang'onyo

Online Theses and Dissertations

A direct analysis in real time mass spectrometry method was developed and validated for the analysis and quantitation of sugars that would be generated from pretreated and hydrolyzed switchgrass. This research aspect can be divided into two sections:

i) Literature Review: A review is presented on the status of energy security and how biomass and biofuels can be utilized as a source of transportation fuel. To this end, biomass (specifically switchgrass) can be broken down by pretreatment methods and then enzymatically hydrolyzed to simple sugars. These sugars can assist with algae growth that can eventually be converted into biofuels. …

Water-Soluble Bis(1,10-Phenanthroline) Octanedioate Cu2+ And Mn2+ Complexes With Unprecedented Nano And Picomolar In Vitro Cytotoxicity: Promising Leads For Chemotherapeutic Drug Development, Andrew Kellett, Mark O'Connor, Malachy Mccann, Orla Howe, Alan Casey, Pauraic Mccarron, Kevin Kavanagh, Mary Mcnamara, Sean Kennedy, Donald May, Philip Skell, Denis O'Shea, Michael Devereux

Articles

Dinuclear Cu^II and Mn^II bis-phenanthroline octanedioate complexes exhibit rapid, unprecedented nano and picomolar in vitro cytotoxicity against colorectal cancer lines and are less toxic than cisplatin when examined in vivo. The complexes are potent generators of cellular reactive oxygen species, avid DNA binders and induce O₂ dependent cleavage of DNA. The Cu(II) complex was found to have self-cleaving nuclease activity.

Synthesis And Characterization Of Novel Benzovesamicol Analogs, Thaer Assaad

Turkish Journal of Chemistry

Three new racemic vesamicol analogs were successfully prepared in good yields and high purity. All compounds were characterized by both IR and NMR spectroscopy. Compounds (\pm)-5 and (\pm)-6 showed a moderate lipophilicity compared with reference compounds IBVM and DRC140, respectively. However, the lipophilicity of DRC140 and (\pm)-9 showed very similar behaviors.

Synthesis And Spectral Characterization Of A Decavanadate/Chitosan Complex, Violeta Dimitrova Kassabova Zhetcheva, Lilyana Parvanova Pavlova

Turkish Journal of Chemistry

A decavanadate/chitosan complex was synthesized by crosslinking chitosan with decavanadate anions at a pH of 3. The materials were characterized by Fourier transformed infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), absorption spectroscopy (UV-Vis), and transmission electron microscopy (TEM). The spectroscopic results indicated that the decavanadate/chitosan complex was successfully obtained as result of an ionic crosslinking of the chitosan with decavanadate anions.

Assimilable Organic Carbon Generation From Algogenic Organic Matter In Drinking Water, Ji-Hoon Kim, Young-Ju Kim, Tahir Imran Qureshi

Turkish Journal of Chemistry

A study of assimilable organic carbon (AOC) derived from algogenic organic matter in different drinking water resources was conducted. Seasonal changes in the concentration of AOC at Kamafusa Dam were dependent on the algal cell numbers. Variations in AOC concentrations were found to be more reliant on the AOC-P17 component than the AOC-NOX component. The algal culture experiment showed that extracellular organic matter (EOM) released during the growth of Phormidium tenue in M-11 culture medium led to a significant increase in AOC concentration; however, no significant variations of AOC concentration were observed in CT culture medium containing high amounts of …

Synthesis And In Vitro Antimycobacterial Activities Of Novel 6-Substituted-3(2h)-Pyridazinone-2-Acetyl-2-(Substituted/ Nonsubstituted Acetophenone) Hydrazone, Semra Utku, Mehtap Gökçe, Gönül Aslan, Gül Bayram, Mahmut Ülger, Gürol Emekdaş, Mustafa Fethi̇ Şahi̇n

Turkish Journal of Chemistry

The difficulty in managing tuberculosis includes the prolonged duration of the treatment, the emergence of drug resistance, and coinfection with HIV/AIDS. Tuberculosis control requires new drugs that act on novel drug targets to help in combating resistant forms of Mycobacterium tuberculosis and reduce the treatment duration. For this purpose, 6-substituted-3(2H)-pyridazinone-2-acetyl-2- (substituted/nonsubstituted acetophenone) hydrazone derivatives were synthesized and their structures were elucidated by elemental analyses, IR, and ^1H-NMR. The in vitro antimycobacterial activities of synthesized compounds 5a-l were determined by the agar proportion method against Mycobacterium tuberculosis H37Rv. Among the target compounds, 5b and 5f exhibited the best antimycobacterial activity, with …

One Pot Synthesis Of Pyridophenanthroline And Pyrrolophenanthroline Derivatives By Regioselective Reaction Between 1,7-Phenanthroline And Dialkyl Acetylenedicarboxylate: New Fused Heterocyclic Compounds, Malek Taher Maghsoodlou, Reza Heydari, Sayyed Mostafa Habibi Khorassani, Batool Tahami Pour, Ghasem Marandi, Farhad Maghfuri

Turkish Journal of Chemistry

1,7-Phenanthroline reacts with dialkyl acetylenedicarboxylate in a regioselective manner to give new macromolecules such as tetramethyl- 6aH-pyrido[1,2-i][1,7]phenanthroline-7,8,9,10-tetracarboxylate and trialkyl pyrrolo[1,2-i][1,7]phenanthroline-7,8,9-tricarboxylate derivatives.

A Near-Infrared Fluorescent Sensor For H^+ In Aqueous Solution And Living Cells, Aibin Wu, Liping Duan

Turkish Journal of Chemistry

A heptamethine cyanine-based sensor (1) was designed and synthesized by incorporating heptamethine cyanine fluorophore and methylpiperazine. Sensor 1 exhibited good response to the change of pH levels, and a large Stokes shift (>100 nm) was obtained. Fluorescent image experiments in living cells further demonstrated its potential applications in biological systems.

Simultaneous Determination Of Dopamine, Uric Acid, And Folic Acid By A Modified Tio_2 Nanoparticles Carbon Paste Electrode, Mohammad Mazloum Ardakani, Mohammad Ali Sheikhmohseni, Hadi Beitollahi, Ali Benvidi, Hossein Naeimi

Turkish Journal of Chemistry

The electrochemical behavior of dopamine (DA) was studied at the surface of a 2,2-[1,2 buthanediylbis(nit- riloethylidyne)]-bis-hydroquinone/TiO_2 nanoparticles modified carbon paste electrode (BQTMCPE) in aqueous media using voltammetric and chronoamperometric techniques. It was found that under optimum conditions (pH 8.0), the oxidation of DA at the surface of such an electrode occurred at about 220 mV lower than that of an unmodified carbon paste electrode (CPE). Using differential pulse voltammetry (DPV), a highly selective and simultaneous determination of DA, uric acid (UA), and folic acid (FA) was explored at the modified electrode. DPV peak currents of DA, UA, and FA increased …

Integrated Modular Microfluidic System For Forensic Alu Dna Typing, Samuel Kimani Njoroge

LSU Doctoral Dissertations

Driven by the numerous applications of genome-related research, fully integrated microfluidic systems have been developed that have advanced the capabilities of molecular and, in particular, genetic analyses. A brief overview on integrated microfluidic systems for DNA analysis is given in Chapter 1 followed by a report on micro-capillary electrophoresis (µCE) of Alu elements with laser-induced fluorescence (LIF) detection, in which the monomorphic Alu insertions on the X and Y chromosomes were utilized to detect male DNA in large female DNA background (Y: X = 1:19) without cell sorting prior to the determination. The polymorphic Alu loci with known restricted geographical …

Fabrication Of Organosilane Nanostructures As Selective Sites For Surface Chemical Reactions, Kathie Lee Lusker

LSU Doctoral Dissertations

Naturally self-assembled mesospheres provide a practical route for controlling the arrangement of materials on surfaces at the nanoscale. Periodic arrays of well-defined nanostructures can be produced with different nanomaterials and interpattern spacings. Results presented in this dissertation demonstrate particle lithography methods developed for fabricating arrays of organosilane nanostructures. Surfaces were designed for the selective deposition of polymers and nanoparticles to produce multicomponent nanopatterns. The approaches for surface patterning provide new directions for studying surface chemistry at the molecular-level, and have practical application for emerging photovoltaic thin film technologies. Atomic force microscopy (AFM) provides unique capabilities for molecular visualization and ultrasensitive …

Proteomic Analysis Of The Blood Of Alligator Mississippiensis, Lancia Nadinia Fallen Darville-Bowleg

LSU Doctoral Dissertations

My research focus was to investigate alligator blood using mass spectrometry-based proteomics methods to understand their innate immune systems. The first goal was to sequence peptides and proteins from the blood serum and leukocytes using tandem mass spectrometry and de novo sequencing. The second goal was to determine the function of these biological molecules and their relationship to the immune system. One- and two-dimensional gel electrophoresis was used to separate proteins from alligator leukocytes, which were enzymatically digested. The peptides were measured using reversed phase nano-high performance liquid chromatography coupled with tandem mass spectrometry (nano-HPLC-MS/MS) followed with de novo sequencing. …

Analysis Of Amyloid Beta (A [Beta]) Peptides By Capillary Electrophoresis And Laser-Induced Fluorescence Anisotropy Detection, Ryan Andrew Picou

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop laser-induced fluorescence anisotropy (LIFA) detection for detecting and characterizing amyloid beta (Aβ) peptide aggregates separated by capillary electrophoresis (CE). Senile plaques composed primarily of aggregated Aβ (1-40) and Aβ (1-42) peptides have been found in the brains of Alzheimer’s disease patients. These peptides are thought to be responsible for the disease pathology. A CE method using UV absorbance detection was developed for the quantification of Aβ (1-40) monomer and testing of Aβ monomer preparations for undesired aggregates (Chapter 2). Analyses of both Aβ (1-40) and Aβ (1-42) monomer …

Formation And Stabilization Of Combustion-Generated Environmentally Persistent Free Radicals On Transition Metal Oxides Supported On Silica, Eric Warren Pimentel Vejerano

LSU Doctoral Dissertations

The formation of environmentally persistent free radicals in combustion system was investigated from chemisorptions of chlorine- and hydroxy-substituted benzenes on transition metal oxide surface under post-combustion conditions. This manuscript reports the formation of EPFRs on silica particles containing 5% Fe(III)2O3, Ni(II)O, and Zn(II)O. The EPFRs are formed by the chemisorption of substituted aromatic molecular adsorbates on the metal cation center followed by electron transfer from the adsorbate to the metal ion at temperatures from 150 to 400 oC. Depending on the nature of the adsorbate and the temperature, two organic EPFRs were formed: a phenoxyl-type radical, which has a lower …

Redox-Active Liposome Delivery Agents With Highly Controllable Stimuli-Responsive Behavior, Nicole Hollabaugh Carrier

LSU Doctoral Dissertations

Over the last few decades, liposomes have generated a lot of interest as drug delivery vehicles to address the need for providing both increased therapeutic efficacy and decreased systemic exposure, simultaneously. The challenge of increasing drug accumulation at diseased sites, without compromising the integrity and stability of the liposomal carrier during circulation, has been met with two possible solutions: (1) active targeting and (2) active triggering. To achieve selective and site-specific delivery of drugs to tumors, active triggering methods have been developed wherein a responsive element is incorporated into the liposomal bilayer, which causes destabilization of the liposome upon exposure …