Chemistry Commons^™

Biosynthesis Of Marineosin, A Spiroaminal Undecylprodiginine Natural Product, Shaimaa Mohamed Salem

Dissertations and Theses

Marineosins A and B are two spiroaminal-ring containing tripyrrole compounds isolated from the marine actinomycete, Streptomyces CNQ-617, and were found to possess potent and selective cytotoxic activity against leukemia and melanoma. Marineosins belong to the prodiginines class of natural products, examples of which are undecylprodiginine and streptorubin B. Unlike marineosins, prodiginines structures are characterized by the presence of fully conjugated tripyrrole nucleus linked to an alkyl chain (that lacks any oxygen). Cyclic prodiginines arise from an oxidative cyclization of the alkyl chain onto the tripyrrole, a step catalyzed by Rieske-oxygenase like enzymes such as RedG. The biosynthesis of prodiginines is …

Understanding The Emission From Semiconductor Nanoparticles, Beth Ann Manhat

Dissertations and Theses

This dissertation describes the synthesis and characterization of fluorescent semiconductor nanoparticles (NPs) in order to optimize their biomedical utility for imaging and sensing applications. While both direct and indirect bandgap semiconductor NPs have been studied, control over their emission properties vary. Quantum confinement (QC), which primarily controls the emission wavelength of nanosized semiconductors, dictates that as the size of semiconductor NPs decrease, the magnitude of the bandgap increases, resulting in changes in the observed emission wavelength: smaller NPs have a larger bandgap, and thus a bluer emission. However, surface, interfacial, or shell defects can act as non-radiative or radiative recombination …

Synthesis And Characterization Of Pbte Quantum Dots, Faiza Anwar

Dissertations and Theses

No abstract provided.

Synthesis Of Alkynyl Ribofuranosides, Christian Rodriguez

Dissertations and Theses

No abstract provided.

Investigation Of The Sources And Sinks Of Atmospheric Methane, Christopher Lee Butenhoff

Dissertations and Theses

The work presented here represents a number of independent studies that investigated various components of the CH₄ budget, namely the sources and sinks. We used a chemical-tracer model and created unique long-term time series of atmospheric CH₄, carbon monoxide (CO), molecular hydrogen (H₂), and methylchloroform (CH₃CCl₃) measurements at marine background air to derive histories of atmospheric hydroxyl radical (OH) - the main chemical oxidant of CH₄, biomass burning - an important source of CH₄ in the tropics, and emissions of CH₄ from rice paddies - one of …

Selective Adsorption Of Dibenzothiophenes On Activated Carbons With Metal Species Deposited On Their Surfaces, Jakub Lison

Dissertations and Theses

"The objective of this thesis is an investigation of influence of porosity, surface chemistry, material composition and effects of metals oncarbon adsorbents in desulfurization of liquid fuels. Materials are derived from poly (4-styrenesulfonic acid-co-maleic acid) salts (sodium or transition metals). They are investigated in a dynamic breakthrough process using model diesel fuel containing dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (DMDBT). The performance of adsorbents is evaluated in terms of the capacity and selectivity. Differences in performance are investigated considering the porosity, surface chemistry and the type of material used."

Modular Synthesis Of Weinreb Amides Of 2-Fluoro-2,4-Dienoic Acids, Mohammad Chowdhury

Dissertations and Theses

No abstract provided.

S-Nitrosothiols: Formation, Decomposition, Reactivity And Possible Physiological Effects, Moshood Kayode Morakinyo

Dissertations and Theses

Three biologically-active aminothiols cysteamine (CA), DL-cysteine (CYSH) and DL-homocysteine, were studied in this thesis. These aminothiols react with nitrous acid (HNO₂), prepared in situ, to produce S-nitrosothiols (RSNOs): S-nitrosocyteamine (CANO), S-nitrosocysteine (CYSNO) and S-nitrosohomocysteine (HCYSNO). They also react with S-nitrosoglutathione (GSNO) and S-nitroso-N-acetylpenicillamine (SNAP) through a transnitrosation reaction to produce their corresponding RSNOs. A detailed kinetics and mechanistic study on the formation of these RSNOs and their subsequent decomposition to release nitric oxide (NO) were studied.

For all three aminothiols the stoichiometry of their reaction with nitrous acid is strictly 1:1 with the formation of one mole …

Electron Transport And Sensor Characteristics Of Tin Dioxide Based Nanocrystalline Materials, Allen Chaparadza

Dissertations and Theses

Wide band gap, transparent semiconductor Sn0₂ is an n-type conductor and is widely used as a sensor material as well as transparent electrode material e.g. in solar cells and flat panel displays. Recent discovery of p-type doping with Li has opened exciting possibilities in new classes of sensors and transparent nanoelectronic devices. Li-doping in SnO₂ nanoparticles was explored through a gel-sol method of synthesis to examine the influence of reaction conditions such as pH, dopant concentration, and calcination temperature. The Li doping in nanoparticles was characterized using nuclear reaction analysis and the nanostructure with high-resolution electron transmission microscopy …

Characterization Of Putative Self-Resistance Genes In The Biosynthetic Gene Cluster Of Hygromycin A From Streptomyces Hygroscopicus Nrrl 2388, Vidya Dhote

Dissertations and Theses

Streptomyces hygroscopicus NRRL 2388 produces an aminocyclitol antibiotic called hygromycin A (HA), which targets bacterial protein synthesis by inhibiting the peptidyl transferase reaction. The hyg6, hygl9, hyg21, hyg28, and hyg29 genes in the biosynthetic gene cluster of HA are predicted to confer self-resistance to the producer strain by different mechanisms. Targeted gene disruptions and in vitro characterization of recombinant proteins were carried out to elucidate the functions of these genes. The hyg21 gene encodes an O-phosphotransferase with a proposed role in HA inactivation by phosphorylation. Disruption of hyg21 led to a significant decrease in HA production but did not …

Synthesis Of Aptamer-Porphyrin Conjugate For Photodynamic Therapy & Synthesis And Stability Of Mixed Thiol/Lipid Coated Gold Nanoparticles, Sarita Sitaula

Dissertations and Theses

An underlying problem in Photodynamic Therapy (PDT) is low selectivity of photosensitizers currently being used for the treatment of tumors. This thesis is focused on developing new PDT drugs and is divided into two parts. The first chapter describes a method for selective delivery of the photosensitizers to the tumor site by conjugating porphyrins to an aptamer for the targeted PDT. To achieve this, a novel synthesis of 2'-porphyrin-modified uridine was developed. The 3'-H-phosphonate derivatives of both 2'-porphyrin and 2'-dithiaporphyrin modified uridine were also synthesized. The 3'41-phosphonate derivative of 2'-porphyrin-modified uridine was conjugated to a 19-mer DNA and to a …

The Original Build Up Of Genetic Information By Rna Recombination, Eric John Hayden

Dissertations and Theses

This research demonstrates chemical reactions of RNA molecules that allow them to increase in length, from non-catalytic oligomers to complex RNA enzymes. The purpose of this research was to explain the origin of large RNA polymers required for life to begin in the proposed "RNA World". To do this, the Azoarcus group I ribozyme was engineered to catalyze phosphodiester exchange reactions that result in the recombination of short oligomer substrates marked by ^5'CAU^3' recognition tags.

To demonstrate the ability to produce catalytic RNA sequences through recombination, substrate oligomers were synthesized that could produce ribozymes if large portions of …

Nanostructered Aminophenylporphyrin Films For Use In Bulk Heterojunction And Inverse Dye-Sensitized Tio₂ Solar Cells, Michael George Walter

Dissertations and Theses

Conductive nanostructured films of poly-tetrakis-5,10,15,20-(4-aminophenyl)porphyrin (TAPP) can be grown electrochemically or through interfacial oxidative polymerization. The poly-TAPP nanomorphology is sensitive to the electrochemical solvent, potentiometric method, and the aminophenyl porphyrin monomer utilized. To elucidate the molecular structure of poly-TAPP and to correlate structures with proposed polymerization and conductivity mechanisms, reflectance FT-IR and spectroelectrochemistry were used to detect the presence and electroactivity of dihydrophenazine and phenazine polymer linkages formed during the polymerization.

Poly-TAPP nanofiber films were evaluated for use in a bulk heterojunction solar cell (with PCBM) and in an inverse dye-sensitized TiO2 solar cell using the poly-TAPP nanoporous scaffold to …

Design And Synthesis Of Antimalarial Drugs Based On A Chloroquine Scaffold, Steven James Burgess

Dissertations and Theses

There are between 350 and 500 million clinical cases of malaria each year, and over 1 million deaths, with pregnant women and children under the age of 5 being most at risk. Chloroquine (CQ) became the preferred drug to treat malaria in the late 1940s, but is now rendered mostly ineffective in many parts of the world, due to widespread CQ resistance by the malaria parasite. All other malaria treatments suffer from some drawbacks, which include development of resistance, side effects including toxicity, risk for pregnant women and young children, and high cost. Some existing, non-antimalarial, drugs have been found …

A Novel Approach To The Synthesis Of Silicon Nanowires, Joo Chick Chan

Dissertations and Theses

Contemporary VLS-SiNW synthetic methods employ CVD and laser ablation methods that produce single crystalline SiNW; which can be doped by co-flowing appropriate dopants, such as diborane (p-type) and phosphine (n-type). Not only are these gases toxic (non-green), but also the synthetic methods used are costly requiring elaborate instrumental assembly. This thesis presents a low-cost and "green" method in synthesizing and doping of SiNW in a glass tube. It was found that by selecting the appropriate metal catalyst, precursor reactants, and the reaction conditions both SiNW and carbon nanotube (CNT) can be synthesized on metallic (aluminum and copper), semiconducting (silicon) and …

Development And Investigation Of Unique Organic Materials To Detect Disease Biomarkers, George Kiplimo Samoei

Dissertations and Theses

Chemomechanical polymer gels with the capability of recognizing specific biological molecules are promising materials for many biomedical applications. Glucose-selective hydrogels have potential utility in the continuous monitoring of glucose and glucose-triggered insulin delivery for the management of diabetes. Herein, the development and study of the first material which detects glucose via significant volume changes in the challenging matrix human blood plasma is described. The material was created via the modification of PMMA with supramolecular binding sites. The polymer exhibits excellent selectivity and reversibility including continuous expansion-contraction cycles.

The Characterization Of Trna Modifying Enzymes S-Adenosylmethionine : Trna Ribosyltransferase-Isomerase (Quea) And A Novel Type I Gtp Cyclohydrolase, Shilah Amal Bonnett

Dissertations and Theses

Queuosine is a hypermodified nucleoside located in the wobble position of bacterial and eukaryotic tRNAs coding for Asp, Tyr, His and Asn. The biosynthesis involves the participation of S-adenosyl-methionine:tRNA ribosyltransferase-isomerase (QueA) and a GTP Cyclohydrolase-I. QueA catalyzes the transfer and isomerization of the ribosyl moiety from AdoMet to preQ1 modified tRNA. Substrate analogs of AdoMet were used to elucidate important substrate-enzyme interactions and to test key steps in the proposed chemical mechanism. Replacing AdoMet with SeAdoMet had little effect upon substrate binding but exhibited 30-fold reduction in kcat, consistent with deprotonation at C-5' as the first catalytic step. 7-deazaAdoMet failed …

Sol-Gel Ph Sensors And Sol-Gel Metal-Removing Sorbents, Dong Liu

Dissertations and Theses

Sol-gel silica is a porous glasslike material that can be prepared at room temperature. In this work, sol-gel method was employed to develop sol-gel sensors for pH measurement and sol-gel silica sorbents for removal of heavy metals.

Sol-gel pH sensors were prepared by entrapping pH indicators in porous solgel silica films. The feasibility of developing optical pH sensors with linear response over a wide pH range by using mixtures of multiple indicators was demonstrated. Theoretical criteria and experimental procedures for selecting indicators and determining optimum ratios of indicators were discussed. A linear response over 4.5 pH units was obtained for …

The Synthesis And Characterization Of A Porphyrin Oligomer As A Potential Antenna For Light Harvesting Solar Cells, Tristan Timothy Jenkins

Dissertations and Theses

Mankind's attempts to harvest the sun have resulted in photocells with about 15% overall energy conversion efficiency. The best of these cells consist of a light-sensitive dye attached to a semiconductor. Absorbed light energy is transferred to the semiconductor via the delivery of an excited electron from the dye. Dye electrons are replenished with a redox solution, coupling the dye to the counter electrode.

This research was the beginning of an exploration into some potential improvements in the cell. First of all, the redox solution is a corrosive liquid, and leaks present a problem. A porphyrin oligomer with a TCPP …

Xanthones As Antimalarial Agents: Binding Interactions Between Heme Analogues And Xanthones, Jane Xu Kelly

Dissertations and Theses

Human falciparum malaria is caused by Plasmodium falciparum parasite, which digests host hemoglobin within its food vacuole, releasing toxic heme. P. falciparum detoxifies free heme to hemozoin by polymerization. This process is believed to be the target of most successful antimalarial drugs, chloroquine and quinine, which are now losing their effectiveness due to the spread of multi-drug resistant strains. Xanthones were recognized in the laboratory of Dr. M. Riscoe (Portland VA Medical Center) to bind to heme, preventing heme polymerization.

This thesis reports a study of the interactions of a potential antimalarial agent, 4,5-dihydroxyxanthone (X2), with heme and tin (IV) …

Paramagnetic Nuclear Magnetic Resonance (Nmr) Studies On The Calcium Binding Site Of [Alpha]-Lactalbumin, Thomas Kurt Ritter

Dissertations and Theses

Paramagnetic NMR has drawn interest as a technique for extending the range of systems that can be investigated. The purpose of this study was to determine whether a combination of paramagnetic two-dimensional and relaxation techniques allows for assigning resonances corresponding to residues forming the metal binding site of proteins in which the metal is coordinated exclusively by amino acid side chains and which have been previously inaccessible to assignment.

α-Lactalbumin (LA) is a calcium binding protein with relatively broad NMR signals; this broadness has prevented complete assignment. LA has been the subject of many studies, because it can form a …

Syntheses And Characterizations Of Unsymmetrical Porphyrins As Photosensitizers For A Solid-State Solar Cell, Yinping Zhao

Dissertations and Theses

Solar light is the most important source of regenerative energy and represents mankind's only inexhaustible energy source. One of today's most promising tools to make use of solar energy is its direct conversion into electrical energy in a photovoltaic cell. The practical use of these solar cells depends on the price of the devices and therefore of the obtained energy. The conventional silicon cells, although efficient, are expensive for common consumer applications. The Grätzel cell is a photovoltaic system for harvesting the sun's energy that operates at about 10-15% overall efficiency, like a conventional solar cell, but does it at …

Efficient Implementation Of Image Compression-Postprocessing Algorithm Using A Digital Signal Processor, Nadir Sinaceur

Dissertations and Theses

In this thesis, an attempt has been made to develop a fast way to implement a post-processing algorithm for image compression. All the previous tests for this postprocessing algorithm, which we will present, have been only software based and did not consider the time parameter.

For this purpose a new algorithm is used to compute the 2-D DCT transform. This change made the process a lot faster on a Spare 5 workstation. We have then decided to further increase the speed of the post-processing scheme by implementing it on the ADSP21020 chip.

The results show that such a chip can …

Synthesis And Characterization Of Novel Sf5 Containing Fluoroalkyl Iodides And Derivatives, Julia Anne Renn

Dissertations and Theses

Preparation of four SF5-containing fluoroalkyl iodides and derivatives thereof was accomplished beginning with a simplified synthesis of ICF2CF2I. Characterization of the products followed using a variety of spectroscopic and physical methods. The simplified method for preparing ICF2CF2I from iodine and tetrafluoroethylene (TFE) involved a reaction temperature of approximately 54°C and pressures of less than two atmospheres for the TFE. The synthesized ICF2CF2I was reacted with S2F1o and tetrafluoroethylene to give SF5CF2CF2I. The subsequent synthesis of the SFs containing fluoroalkyl iodides and derivatives were carried out using SFsCF2CF2I as the starting material in a Carius tube reaction vessel. The synthesized SFs …

Fluorinated Polymer Films: Synthesis And Characterization, Anja Ulrike Schnurer

Dissertations and Theses

Three polyfluoroalkyl epoxides, (I OCH₂CHCH₂OCF₂CF₂SO₂F, II OCH₂CHCH₂(CF₂)₈F and III OCH₂CHCH₂O(CF₂)CF(CF₃)SO₂F) were photopolymerized with a cycloaliphatic diepoxide (Cyracure UVR-6110) to form highly crosslinked glassy films. Depth-dependent surface analysis with XPS show that these films are highly enriched with sulfonyl fluoride groups in the outer molecular surface. Film compositions of 17 % wt and more of the fluorinated I and III show surface characteristics of a film composed of 100 % wt of the …

Nmr Study Of Neurophysin Dimer Dissociation By Cosolvents, Jian Yao

Dissertations and Theses

Neurophysins (NPs) make up a relatively small, stable, and highly soluble class of proteins. They have physiological roles of storage and stabilizing' of peptide hormones oxytocin and vasopression within the posterior pituitary neurosecretory granules. At the concentration of NP found within the granules, NP would exist as a dimer in the absence or presence of bound peptide. The NP monomer-monomer interface involves B-sheet/ B-sheet contact, which can be modulated by the presence of cosolvent. This remarkable feature of NP makes it a model for Alzheimer's disease. One of the characteristics of Alzheimer's disease is the presence of plaques of B-amyloid …

Heme Proton Resonance Assignments And Kinetics Study In High-Spin And Mixed-Spin Metmyoglobin Complexes By Chemical Exchange Nmr Spectroscopy, Ying Luo

Dissertations and Theses

NMR studies of paramagnetic hemoproteins have improved significantly our understanding of the structure-function relationship of hemoproteins in general. Up to date most of the studies focus on low-spin ferric systems which are characterized by relatively narrow resonance peaks and concomitant better resolution.

However, characterizing in detail the NMR spectra of high-spin ferric hemoproteins is important since there are several hemoproteins, such as peroxidases, catalases, oxygenases, and some ferricytochromes that contain high-spin iron (III) in their biologically active forms. Yet assigning resonances from heme peripheral protons and/or heme pocket residues in high-spin myoglobins is a daunting undertaking. Only a sparse number …

Synthesis And Characterization Of Novel Fluorine Containing Alkylsulfonyls And Sulfonates : Fluorinated Sulfonyl Methanes And Derivatives, Nelson R. Holcomb

Dissertations and Theses

A series of salts of the strong fluorocarbon acid bis(trifluoromethylsulfonyl)methane were made: (CF3S02 ) 2CHK, (CF3S02 ) 2CHLi, [ (CF3S02 ) 2CH] 2Ca, [ (CF3S02 ) 2CH] 2Hg, (CF3S02 ) 2CHAg, [ (CF3S02 ) 2CH] 3La. Their reactivity and use as organic intermediates were investigated. The salts were made from their corresponding carbonates, oxides, or hydrides. The reaction times for the salts is generally short, however the purification process was laborious, involving recrystallization from organic solvents and drying under vacuum. The lithium salt is being evaluated as a solid state battery electrolyte. Derivatives of bis(trifluoromethylsulfonyl)methane were made by using the …

Synthesis And Characterization Of A Porphyrin Dyad, Dale A. Braden

Dissertations and Theses

The sun is a bountiful source of energy for our planet. .With the advent of photovoltaic cells, man has begun harnessing the sun's radiant energy, turning it into a form more directly useful: electricity. Commercially available solar cells currently operate at about 13% efficiency, sufficiently high to make them a viable source of electrical energy. It is of great interest, however, to improve their conversion efficiency, and to lower the cost of production so as to make them more economical, and thereby reduce our dependence upon traditional "dirty" sources of energy such as coal and oil. It has been found …

Studies In Fluorine Chemistry: 13c Nmr Investigation Of Sf5/So2f Fluorinated Systems, Yoon S. Choi

Dissertations and Theses

The purpose of this thesis was two fold: (i) The synthesis and characterization of SF5 containing dienes. (ii) The characterization of hydro/fluorocarbon compounds containing SF5/S02F groups via their 13C NMR spectra. A new SF5CH2CHBrCH2CF=CF2 was prepared and characterized as a precursor to new dielectric polymers. This new adduct was made from the reaction of pentafluorothio bromide with l,l,2-trifluoro-1,4-pentadiene. A SF5-diene was prepared from the reaction of pentafluorothio chloride with acetylene. This reaction involves a radical addition mechanism. The SF5 group is bonded to the carbon atom carrying the most hydrogens. SF5 - dienes are capable of undergoing different reactions, such …