Organic Chemistry Commons^™

Efficient Utilization Of Solar Energy In Dye-Sensitized Solar Cells And In The Photocatalytic Reduction Of Carbon Dioxide, Aron Joel Huckaba

Electronic Theses and Dissertations

One of the most important questions humanity will face in the next 100 years is going to be "What will happen when oil runs out?" This dissertation describes efforts to utilize solar energy to improve renewable energy technology in two ways: First, through the improvement of dye sensitized solar cells by theimprovement of D-π-A dye subunits, the development of practical sensitizers, and progress towards stable, tunable redox shuttles. A novel indolizine donor subunit was synthesized that was shown to be the strongest reported donor. Dyes made from this novel donor and devices using the Γ-/I 3- reached up to 5.4% …

Synthetic Study Of Karlotoxins And Investigation Of Alpha-Diaminoboryl Carbanion Chemistry, Yusuke Takahashi

Electronic Theses and Dissertations

Karlotoxins (KmTxs), produced by a toxic marine/estuarine phytoplankton, the dinoflagellate Karlodinium veneficum, are known to be ichthyotoxic, thus being associated with numerous fish deaths events worldwide. They have also been reported to show a variety of biological activities such as hemolytic, cytotoxic, and anti-fungal activities. Recently, the Hamann group successfully assigned the absolute configurations of KmTx2, the first complete structure elucidation among the congeners. In a structural sense, karlotoxins are a family of linear polyketides with three distinctive regions; a bis-tetrahydropyran core fragment, a long, highly oxygenated carbon chain, and a lipophilic chlorodiene unit. Such potent biological activities as well …

Molecular Encapsulation In Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers, Jennifer Christine Chapin Lake

Electronic Theses and Dissertations

Pyrogallolarene and resorcinarene hexamers are hydrogen-bonded capsules that self-assemble in the solid state and can be studied in gaseous and solution phases. Guest loading within pyrogallolarene hexamers in solution has primarily been comprised of solvent molecules with some tertiary amines. A novel solvent-free method for loading guests into the interior of the hexamer has been shown to be effective for encapsulation of a variety of molecules. Aromatic and aliphatic compounds have particularly high guest loading within the hexamers and often result in kinetically stable guest-filled capsules in solution.

Kinetic studies of the encapsulation complexes of anthracene, biphenyl, fluoranthene, fluorene, naphthalene, …

Functionalization Of Silica Surface Using Chan-Lam Coupling, George Appiah Kubi

Electronic Theses and Dissertations

The reaction of base-free Chan-Lam coupling was successfully used for functionalization of surface of mesoporous silica gel. Various aromatic, aliphatic, and heterocyclic compounds were immobilized by a copper-catalyzed reaction of corresponding boronic acids with surface amino groups at mild conditions. Obtained functionalized materials were mesoporous although their surface area decreased after immobilization. The reactivity of some surface functional groups was tested in their characteristic reactions.

Synthesis Of A 4-(Trifluoromethyl)-2-Diazonium Perfluoroalkyl Benzenesuflonylimide (Pfsi) Zwitterionic Monomer For Proton Exchange Membrane Fuel Cell, Chimaroke Nworie

Electronic Theses and Dissertations

In order to achieve a more stable and highly proton conducting membrane that is also cost effective, the perfluoroalkyl benzenesulfonylimides (PFSI) polymers are proposed as electrolyte for Proton Exchange Membrane Fuel Cells. 4-(trifluoromethyl)-2-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide (I) is synthesized from Nafion monomer via a 5-step schematic reaction at optimal reaction conditions. This diazonium PFSI zwitterionic monomer can be further subjected to polymerization. The loss of the diazonium N₂⁺ functional group in the monomer is believed to form the covalent bond between the PFSI polymer electrolyte and carbon electrodes support. All the intermediates and final products …

Synthesis Of Ester Derivatives Of Resveratrol As Potential Anti-Cancer Drugs, Parasmani Pageni

Electronic Theses and Dissertations

Resveratrol is a naturally occurring phytoalexin of the stilbene family produced by various plants in response to stress, UV radiation, and fungal attack. It is primarily found in peanuts, berries, grape skin, and red wine. Resveratrol has been found to exhibit anti-cancer, anti-inflammatory, anti-aging, and anti-oxidant properties. Research indicates that diets enriched with resveratrol containing substances result in less incidence of cancer. Unfortunately, the low bioavailability and solubility has been a huge setback for its potential prospects. As a result, efforts have been made to synthesize derivatives of resveratrol with increased solubility and bioavailability. Three triester novel resveratrol derivatives 3, …

Design And Synthesis Of Novel Fluorescent Nucleoside Analogues, Nada Abdulnasir Elsharif

Electronic Theses and Dissertations

This project aimed to obtain a set of fluorescent nucleoside analogues that closely resemble cytosine with extending the aromatic surface (extended conjugation) for enhance the photophysical properties. In addition to synthesize new fluorescent nucleoside analogues and evaluate their photophysical properties, this project aimed to understand the effects of donor substituent on the tC photophysical properties.

The main goal of these studies is to develop highly fluorescent nucleotide analogues. We first were looking to synthesize tC^C fluorescent nucleotide with the pyrimido[4,5-b]quinolone. In this part, 2-chloro-3- formylquinoline was easily prepared, yet the cyclization of 2-chloro-3- formylquinoline with urea or guanidine HCl …

Donor-Sigma-Acceptor (D-Sigma-A) Molecules With Perylenebisimide Acceptors Having Alkyl Or Peg Swallowtails With Sulfur Or Hydroxyl Anchors: Synthesis And Applications In Langmuir-Blodgett Films, Single Molecule Spectroscopy (Sms), G-Quadruplex Studies And Passivation Of Gold Nanoparticles, Rajesh Kota

Electronic Theses and Dissertations

Use of single molecules as electronic devices is presently considered a potential alternative to semiconductor-based nanoscale electronics. The ability to study a single molecule or a small group of molecules provides a great opportunity to build electronic devices at the molecular level. It is vital to understand the parameters that control the device properties such as molecular structure, conformation and arrangement at the surface. Ari Aviram and Mark A. Ratner proposed the construction of a single organic molecule as an organic rectifier. Donor-Sigma-Acceptor (D-?-A ) molecules, when arranged with a proper orientation as Langmuir-Blodgett (LB) films and fixed between two …

Synthesis Of Chemical Models Of Hydrolase Enzymes For Intramolecular Catalysis., Cornelius Ndi Ndi

Electronic Theses and Dissertations

Most nuclease enzymes can hydrolyze phosphoester bonds (in DNA and RNA) by using metal ions cofactors that coordinate and activate water molecules in the enzymes' active sites. However, there are some hydrolase enzymes (including nucleases) that can function without the aid of metal ions. 2,6-Di(1H-imidazol-2-yl)phenol, a model compound for hydrolase enzyme, was synthesized by the reaction between ethylenediamine and dimethyl-3-carboxysalicylate, initially resulting in the formation of diimidazoline. The diimidazoline was subsequently aromatized to the diimidazole by dehydrogenation over palladium. The overall reaction yield was low; therefore, other dehydrogenation transformation reactions were tried but all failed to improve the …

Design And Synthesis Of Novel Agrofungicides Based On Naturally Occurring Pbdes, Robert Alexander Smith

Electronic Theses and Dissertations

Cyanobacterial symbionts of Indo Pacific marine sponges, e.g. Dysidea sp., produce hydroxylated (OH-) polybrominated diphenyl ethers (PDBEs) which likely function as chemical deterrents owing to their antifungal and antibacterial properties. Limiting the therapeutic potential and agricultural use of these antimicrobial natural products are the negative connotations associated with non hydroxylated anthropogenic PBDEs. Anthropogenic PBDEs are pervasive global pollutants used as flame retardant additives in many household goods, e.g. furniture, textiles, and electronics. These molecules have a propensity to bioaccumulate in living organisms, they easily traverse the trophic food chains, they are readily passed from mother to offspring, and many of …

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 …

Novel Photochemical Methodologies For Diversity Oriented Synthesis And Screening Of Combinatorial Libraries, Roman Askatovich Valiulin

Electronic Theses and Dissertations

The main goal of this project was to develop an efficient methodology allowing rapid access to structurally diverse scaffolds decorated with various functional groups.

Initially, we discovered and subsequently developed an experimentally straightforward, high-yielding photoinduced conversion of readily accessible diverse starting materials into polycyclic aldehydes and their (hemi)acetals decorated by various pendants. The two step sequence, involving the Diels-Alder addition of heterocyclic chalcones and other benzoyl ethylenes to a variety of dienes, followed by the Paternò-Büchi reaction, was described as an alkene-carbonyl oxametathesis. This methodology offers a rapid increase in molecular complexity and diversity of the target scaffolds.

To develop …

Approaches Towards The Synthesis Of Bradyoxetin, Vanildo Martins Lima Braga

Electronic Theses and Dissertations

Quorum sensing bacteria produce and release chemical signal molecules (like N-acyl homoserine lactones, AHL) that increase in concentration as a function of cell density. The responses cover a large spectrum of process such as the virulence in Staphylococcus aureus, competence for DNA-uptake in Bacillus subtilis and Streptococcus pneumoniae, sporulation in Bacillus subtilis, conjugal plasmid transfer in Enterococcus faecalis, and bacteriocin production in lactic acid bacteria. The collapse of (AHL) signaling system in bacteria represents an attractive therapeutic approach towards the development of new antibiotics. Recently, a new extracellular modulator was isolated from a symbiotic bacterium (Bradyrhizobium japonicum) that nodulates soybean. …

Determination Of The Activation Parameters Of Reaction Between [Fe(Cn6]-4 And K[Co(Hedta)No2]., Sammy Eni Eni

Electronic Theses and Dissertations

The kinetics of the oxidation of [Fe(CN)₆]^-4 by K[Co(HEDTA)NO₂] was studied in order to get the mechanism and the activation parameters of the reaction. Using a freshly-made Na₃PO₄ solution as the reaction medium with a pH of 6.00 the ionic strength was maintained at 0.10 M and the buffer molarity was 0.001 M.

The rate constant (k_obs) of the reaction between [Fe(CN)₆]^-4 and K[Co(HEDTA)NO₂] was determined at temperatures of 25.0°C, 27.5°C, 30.0°C, 35.0°, and 40.0°C. We explored this reaction by monitoring the evolution of ferricyanide, …

Novel Strategy For The Synthesis Of Allenes., Mark-Henry Mbahmi Kamga

Electronic Theses and Dissertations

Allenes are very important chemical reagents in organic synthesis. Due to their high reactivity, they have been extensively used to carry out a variety of unique and effective chemical transformations including but not limited to ionic and free radical additions and transition metal catalyzed cyclizations. As the chemistry of this group of compounds is explored further and their applications expanded there is a need to develop alternative and cost effective methods for their synthesis. Our approach involves the synthesis of allenes from oxa-bicyclo-alkan-2-ones by methyllithium induced Eschenmoser fragmentation of the bicyclotosylhydrazone derivatives.

Towards The Design And Syntheses Of Novel Triads Comprising Single Robson-Type Macrocyclic Dicopper(Ii) Cores Flanked By Two Terminal Polypyridyl Ruthenium(Ii) Complexes., Leslie Shane Moody

Electronic Theses and Dissertations

Progress toward the syntheses of new tetranuclear bimetallic complexes of copper(II) and ruthenium(II) was realized. The designed triads comprise a central binuclear copper(II) complex with a tetraiminodiphenolate macrocyclic Robson-type compartmental ligand. In the envisioned complexes, the macrocyclic core is further functionalized by attachment of two polypyridyl ruthenium(II) complexes. A novel dibrominated dicopper(II) Robson complex was formed by the 2:2:2 condensation reaction of 4-bromo-2,6-diformylphenol and 1,3- diaminopropane with cupric chloride. Similarly, a new dibrominated dizinc(II) was synthesized from zinc tetrafluoroborate and the same diamine and dialdehyde. The new dicopper(II) complex did not heterocouple with borylated substrates under explored Suzuki reaction conditions. …

Contraction-Expansion Protocols., Nadine Katia Njoya

Electronic Theses and Dissertations

An approach to a new class of compounds known as bridgehead dienone is described. The route is based on a tandem contraction-expansion event in which the contraction triggers the expansion. The two steps involved are a palladium-catalyzed Favorskii contraction and a cis-divinyl cyclopropanone rearrangement. Progress towards these goals is reported.

Synthesis Towards Fulminic Acid And Its Derivatives In 1, 3-Dipolar Cycloaddition Reactions., Ophilia Ndi Toh

Electronic Theses and Dissertations

A new approach to fulminic acid cycloadditions has been developed. At reduced temperatures, fulminic acid is generated in situ and undergoes 1, 3-diploar cycloaddition reactions with dipolarophiles to form isoxazolines and/or its dimers. This procedure represents a novel, safe general method for the one-step generation of fulminic acid, which complements existing potentially explosive protocols.

Cell Toxicology Study Of Rrr-Alpha-Tocopheryl Polyethylene Glycol 1000 Succinate (Tpgs)., Clarisse Sornsay Muenyi

Electronic Theses and Dissertations

This research focused on the cytotoxic properties of RRR-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS) in transformed and cancerous cell lines. We used RAW264.7 macrophage and prostate cancer (LNCaP) cell lines in this study. TPGS caused cell death and decreased cell viability in a dose and time dependent manner. Cell death was evaluated fluorimetrically by employing the nucleic acid-binding fluorophore; propidium iodide. A colorimetric 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay was used to evaluate cell viability. Cell death can occur through necrosis or apoptosis. Our results suggested that TPGS triggered apoptotic cell death. Induction of apoptosis, as measured by caspase …

Cell Toxicity And Uptake Of Rrr-Alpha-Tocopheryl Polyethylene Glycol 1000 Succinate (Tpgs) By Various Cell Ines In Vitro., Christelle Komguem Kamga

Electronic Theses and Dissertations

This research focused on investigating and comparing the cytotoxicity and cellular uptake of RRR-alpha-tocopheryl polyethylene glycol succinate (TPGS, with that of alpha-tocopheryl succinate (α-TS). Both TPGS and α-TS are water-soluble forms of vitamin E with important clinical applications. Cytotoxicity assays with RAW 264.7 and LNCaP cells incubated overnight with TPGS or α-TS at concentrations ≥ 12.4 μM suggest that α-TS is more cytotoxic than TPGS. Macrophages were found to be more sensitive than LNCaP cells when treated with similar concentrations of α-TS. For both cell lines, most of the TPGS or α-TS taken up remained esterified after 24 hours. Our …

Structural Study Of Disease Related Proteins, Ayse Sinem Ozyurt

Electronic Theses and Dissertations

The availability of complete sequences for the genomes of many organisms changes the researcher's attention from genome sequencing to finding the function of gene products, the proteins. The three dimensional (3D) structure of a protein is helpful to understand its function, because tertiary structure is more conserved in evolution than sequence. The 3D structures can be found quickly by using high-throughput (HT) methods for protein expression, purification, characterization and structure determination. This process is very challenging in every step. Therefore we selected nearly 200 cancer related proteins as targets to see the difficulties in trying to determine the web predicted …

A Study Of Bisimines Of Tetramethyl-1,3-Cyclobutanedione, Edward Albert Schmidt

Electronic Theses and Dissertations

It was the purpose, therefore, of this work, to investigate the preparation, properties, and reactions of bisimines of 2,2,4,4- tetramethyl-1,3-cyclobutanedione, to determine the chemical effects of carbon π-bonded to nitrogen. Certain of these effects are compared to carbon π-bonded to oxygen in a structurally similar environment.

The Chemistry Of Some Unusual Carbodiimides, Donald Melvin Plautz

Electronic Theses and Dissertations

Several N¹-alkyl-N²-(N,N-dialkylamino)carbodiimides, which were found to form dimeric species, were prepared, and the structure of the dimeric species determined. A study of the reaction chemistry of both the monomeric and dimeric carbodiimides led to the conclusion that dimerization occurred via a (π2s + π2a) ground-state, symmetry-allowed mechanism, and that thermal decomposition of the dimeric species occurred via a (π2s +-π2s) excited-state, symmetry-allowed mechanism. Although dialkylphosphoramidates have been shown to be useful intermediates in the preparation of unsaturated organic nitrogen compounds, N-acyl- and N-imino-dialkylphosphorohydrazidates were found to be too unstable, forming trialkylphosphates upon distillation, to be of …

Itaconic Acid Derivatives Of P-Amino Alkyl Sulfone, Wilbur B. Clarke

Electronic Theses and Dissertations

This investigation is concerned with the preparation of 1(p-R1 Sulfonyl)-phenyl-5-oxo-3-pyrrolidine carboxylic acid by direct fusion of itaconic acid with the respective p-Amino phenyl alkyl or aryl sulfone, and its continuation of work previously reported

Itaconic Acid Derivatives Of P-Amino Alkyl, Alkyl Sulfone, Wilbur B. Clarke

Electronic Theses and Dissertations

This investigation is concerned with the preparation of 1(p-R2 Sulfonyl)-phenyl-5-oxo-3-pyrrolidine carboxylic acid by direct fusion of itaconic acid with the respective p-Amino phenyl alkyl or aryl sulfone, and is a continuation of work previously reported.

Itaconic Acid Derivatives Of Sulfanilamide And Sulfone, Malcolm J. Thompson

Electronic Theses and Dissertations

This thesis, submitted to Xavier University in partial fulfillment of requirements for a Maters degree in chemistry in 1952, reports the synthesis and characterization of itaconic acid derivatives of sulfanilamide and amino phenyl sulfone compounds. The research describes reaction procedures and the isolation and purification of a series of novel chemical compounds, with experimental data including melting points, percent yields, elemental analysis, and molecular weights reported for numerous derivatives. The thesis presents conclusions regarding the chemical properties and reactivity of the synthesized compounds.

Note: No original abstract was included; this abstract is provided by the XULA Digital Commons editors.

Separation Of The Selenium Compounds In Seleniferous Plant Protein Hydrolysates By Paper Partition Chromatography, Arnold L. Smith

Electronic Theses and Dissertations

In 1943 Franke reported that the protein of "allolied" or "toxic" wheat carried the toxicant, and Franke and Painter in 1935 reported that those "toxic" proteins contained selenium which was in organic combination in the protein. There has been much speculation regarding the possibility of selenium replacing sulfur in the amino acids cysteine and methionine. The toxicity of selenium in selenium analogs of these compounds is similar to that of selenium occurring naturally in proteins seleniferous cereals, which indicated that the selenium may be present in the proteins as the analogue of these sulfur amino acids.

A Study Of Factors Influencing The Hydrolysis Of Corn Amylopectin By Barley Malt Enzymes., Thelma Munsey Back 1918-2006

Electronic Theses and Dissertations

No abstract provided.

The Alkaloids, Felix F. Barre

Electronic Theses and Dissertations

This thesis, presented for the degree of Bachelor of Science, provides a systematic chemical study of the alkaloids, a class of complex nitrogenous plant substances possessing basic properties. Barre opens by defining the alkaloids and surveying the various systems used to classify them, whether by natural versus artificial origin, chemical nucleus (pyridine, quinoline, or isoquinoline), volatility, or botanical family of origin, and outlines their general physical and chemical properties, including solubility, optical activity, and characteristic reactions with precipitating and color-test reagents.

The thesis details standard laboratory methods for the extraction and separation of alkaloids from plant material, including a step-by-step …