Organic Chemistry Commons^™

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 …

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 …

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 …

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 …

Effect Of A Strategically Positioned Methoxy Substituent On The Photochemistry Of 3-Aryl-3h-1-Oxacyclopenta[L]Phenanthren-2-Ones, Roshini Thumpakara, Binoy Jose, Perupparampil Unnikrishnan, Sreedharan Prathapan, Nigam Rath

Chemistry & Biochemistry Faculty Works

Irradiation of 3-methoxy-3-aryl-3H-1-oxacyclopenta[l]phenanthren-2-one derivatives 5a–d resulted in singlet-mediated decarbonylation reaction leading to the formation of phenanthrene derivatives 9a–d. The structure of the photoproduct was unequivocally established on the basis of X-ray crystallographic analysis.

Conjugate Additions And Transposition Of The Allylic Alcohols Of Enol Ethers Of 1, 2-Cyclohexanedione., Barnabas Otoo

Electronic Theses and Dissertations

A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one …

Investigation Of Volatile Products From Wood Pyrolysis, Prabhavathi Gade

Masters Theses & Specialist Projects

In this research we are following the thermo-chemical degradation of wood in the absence of oxygen. The objectives are to evaluate the influence of heating rates on pyrolysis products obtained from wood pyrolysis and to evaluate the influence of acid pre-treatment on pyrolysis products. Depending on the wood heating rates, pyrolysis can be categorized as Flash pyrolysis, Fast pyrolysis, and Slow pyrolysis. We have evaluated the volatile products obtained at different heating rates and the volatile products obtained from sulfuric acid pre-treatment by using gas chromatography- mass spectrometry (GC-MS). We have also performed thermo-gravimetric analysis (TGA) of raw wood samples …

Two-Phase Partitioning System Using Elvax 40w Polymer For The Biodegradation Of Aqueous Phenols, Amit Suresh Ghode

Masters Theses & Specialist Projects

A solid-liquid two phase partitioning system (TPPS) is a new technology platform for destroying toxic organic compounds. TPPS have traditionally been operated by using an immiscible organic phase which partitions organic compounds into the aqueous phase. TPPS using an immiscible organic phase suffers from several limitations such as the organic phase could be biodegradable and hence only certain compatible microbial strains could be used. This therefore, eliminates the desired use of mixed microbial populations for efficient degradation. A solid-liquid two phase partitioning system, in which solid polymeric beads replace liquid organic phase, appears to have benefits over the traditional liquid-liquid …

Iota-Carrageenan Hydrolysis By Pseudoalteromonas Carrageenovora Ifo12985, Bernadette M. Henares, Erwin P. Enriquez, Fabian M. Dayrit, Nina Rosario L. Rojas

Chemistry Faculty Publications

We report iota-carrageenan hydrolysis by Pseudoalteromonas carrageenovora IFO 12985. Kappa-carrageenase and lambda-carrageenase were previously isolated from this organism, but iota-carrageenase activity had not been reported in the literature. P. carrageenovora was grown in iota-carrageenan-based liquid medium. Using the zone of depression assay, transfer of aliquots of the culture to solid medium with 2% iota- and kappa-carrageenan showed extensive hydrolysis of iota-carrageenan. Analysis of the hydrolysates by C-13 Nuclear Magnetic Resonance spectroscopy confirmed degradation of the iota-carrageenan. Hydrolytic activity of P. carrageenovora grown in iota-carrageenan was compared with that of the same organism grown in kappa-carrageenan. Cell-free supernatants from each yielded …

Ultrasonic Activation Of Triacetone Triperoxide, Latravia R. Dobson

Department of Chemistry: Dissertations, Theses, and Student Research

Triacetone triperoxide (TATP) is an organic peroxide that has received widespread attention in recent years. TATP is a ketone peroxide with a high active oxygen content. It is relatively shock sensitive, with explosive decomposition easily initiated, and is therefore considered a primary explosive. However, TATP is also a powerful explosive possessing about 83 % of the power of TNT. TATP can be prepared quickly and easily from inexpensive household chemicals in the absence of any specialized facilities, making it the explosive of choice for modern day terrorists. TATP poses a major challenge for security and law enforcement services around the …

I, A New Synthetic Approach To The Synthesis Of N-(Phosphonoacetyl)-L-Ornithine. Ii, The Influence Of Pyridine On The Ozonolysis Of Alkenes, Bradley M. Johnson

Department of Chemistry: Dissertations, Theses, and Student Research

Part I. The use of chemical inhibitors to manipulate the level of amino acids in cells has proven to be invaluable in the mechanistic study of gene expression in bacteria and fungi. Here we present a new approach to the synthesis of δ‐N‐ (phosphonoacetyl)‐L‐ornithine (PALO), a potent ornithine transcarbamylase inhibitor, using a new amino acid protecting group, 9‐borabicyclononane (9‐BBN). Starting from commercially available reagents and utilizing mild reaction conditions, we were able to form PALO in fewer synthetic steps and in greater yields than previous attempts.

Part II. Ozonolysis is widely used to transform alkenes into oxygen‐rich functional groups (e.g.– …

Design And Regioselective Synthesis Of Two And Three-Pronged C60 Fullerene Derivatives And Their Applications In Molecular Electronics, Angy Ortiz-Hernandez

All Dissertations

Since the introduction of semiconductors in the second half of the 20th century, advancements in electronics and technology have been tremendous. In particular, the rapid development of silicon-based computer chip technology and miniaturization of electronic components has been tremendous. Since silicon-based materials have a limit in terms of size, scientists proposed that individual molecules could behave as single electronic components for high degree of miniaturization.
Given that the molecules of interest must have dimensions on the nanometer scale, be able to bind to the electrode surface and have electron donor-acceptor properties, C₆₀ fullerene has been a prime candidate for …

Novel Neomycin Conjugates For Multi-Recognition Of Nucleic Acids, Albert Willis

All Dissertations

Neomycin is an aminoglycoside antibiotic known for its high affinity for RNA duplex structures. Recent developments from our labs have indicated that aminoglycoside binding is not limited to RNA, but to nucleic acids that, like RNA, adopt conformations similar to A-form. Our group sought to further expand the utility of aminoglycoside binding to B-DNA structures by conjugating neomycin, an aminoglycoside antibiotic, with the B-DNA minor groove binding ligand Hoechst 33258. Envisioning a dual groove-binding mode, we have extended the potential recognition process to include a third, intercalative moiety. Furthermore, we observe remarkable recognition of such conjugates with RNA duplex. Spectroscopic …

Preparation And Studies Of Fluorescent Carbon Nanomaterials, Xin Wang

All Dissertations

There have been rapid advances in the development and applications of semiconductor quantum dots (QDs) represented by CdSe/ZnS. However, a serious limitation of these QDs is the necessary use of toxic heavy metals. Fluorescent 'carbon dots' (surface passivated carbon nanoparticles) are developed as alternative to classical semiconductor QDs.
The carbon dots could be made to be highly fluorescence, with emission quantum yields close to 60%. Their optical properties resemble bandgap transitions found in nanoscale semiconductors, suggesting that carbon particles at the nanoscale acquire essentially semiconductor-like characteristics.
The fluorescence in carbon dots could be quenched efficiently by electron acceptor or donor …

(1e,3e)-1,4-Bis(4-Methoxyphenyl)Buta1,3-Diene, Gopinathan Narayan, Nigam Rath, Suresh Das

Chemistry & Biochemistry Faculty Works

The title compound, C18H18O2, which exhibits blue emission in the solid state, is an inter­mediate in the preparation of liquid crystals and polymers. The mol­ecule is located on an inversion centre. In the crystal, mol­ecules are arranged in a herringbone motif.

Oga Inhibition By Glcnac-Selenazoline, E. J. Kim, D. C. Love, E. Darout, M. Abdo, B. Rempel, S. G. Withers, Paul R. Rablen, J. A. Hanover, S. Knapp

Chemistry & Biochemistry Faculty Works

The title compound, which differs from the powerful O-GlcNAcase (OGA) inhibitor GlcNAc-thiazoline only at the chalcogen atom (Se for S), is a much weaker inhibitor in a direct OGA assay. In human cells, however, the selenazoline shows comparable ability to induce hyper-O-GlcNAc-ylation, and the two show similar reduction of insulin-stimulated translocation of glucose transporter 4 in differentiated 3T3 adipocytes. (C) 2010 Elsevier Ltd. All rights reserved.

Characterization Of Metastasis-Associated Cell Surface Glycoproteins In Prostate Cancer, Lifang Yang

Theses and Dissertations in Biomedical Sciences

Prostate cancer (PCa) is a major health problem in males in the United States. Its lethality is mostly attributed to the primary tumor metastasizing to distant sites that are highly resistant to conventional therapies. Serum Prostate Specific Antigen (PSA) is the only protein biomarker used in clinic for prediction of prostate cancer recurrence following local therapies. Nonetheless, PSA lacks the ability to predict the behavior of an individual tumor in an individual patient. Therefore, development of reliable biomarkers for detection of metastatic potential in primary tumors, as well as discovery of new therapeutic targets, is in a great need for …

Jahn-Teller Coupling And Fragmentation After Core-Shell Excitation Ini Cf4 Investigated By Partial-Ion-Yield Spectroscopy, Renaud Guillemin, Wayne C. Stolte, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigate fragmentation processes induced by core-level photoexcitation in CF4 at both the carbon and fluorine K edges by means of partial-ion-yield spectroscopy. The molecule CF₄ is a textbook example of systems in which Jahn-Teller coupling strongly manifests itself in the photoabsorption spectrum. Spectral features related to Jahn-Teller and quasi-Jahn-Teller splitting are observed, and important differences in the fragmentation pathways are revealed depending on the symmetries of the core-excited states. We interpret these experimental observations on the grounds of symmetry lowering from the Td to the C3v point group as well as preferential orientation with respect …

4-Phenyl­Sulfon­Yl-2-(P-Tolyl­Sulfon­Yl)-1h,8h-Pyrrolo­[2,3-B]Indole, Jeanese C. Badenock, Jason A. Jordan, Erin T. Pelkey, Gordon W. Gribble, Jerry P. Jasinski

Dartmouth Scholarship

The title compound, C23H18N2O4S2, contains a pyrrolo group fused onto the plane of an indole ring with phenylsulfonyl and p-toluenesulfonyl groups bonded to the indole and pyrrolo rings. The angles between the mean planes of the pyrrolo- indole ring and the phenylsulfonyl and p-toluenesulfonyl rings are 73.7 (6) and 80.6 (0)􏰈, respectively. The dihedral angle between the mean planes of the two benzene rings is 78.7 (4)􏰈. In the crystal, both classical N—H􏰇 􏰇 􏰇O and non-classical C— H􏰇 􏰇 􏰇O intermolecular hydrogen-bonding interactions are observed, as well as weak 􏰁–􏰁 interactions [centroid–centroid distances = 3.6258 (8) and 3.9298 (8) …

I, Development Of The In Situ Reductive Ozonolysis Of Alkenes With Tertiary Amine N-Oxides. Ii, Progress Toward The Asymmetric Synthesis Of Peroxyplakoric Acid A3, Christopher P. Schwartz

Department of Chemistry: Dissertations, Theses, and Student Research

Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is …