Chemistry Commons^™

Sds Non-Acrylamide Polymeric Gel-Filled Capillary Electrophoresis For Molecular Size Separation Of Protein, Devon Andres

Honors Theses

Sodium dodecyl sulfide (SDS) non-acrylamide gel-filled capillary columns are a new technology being used for analysis and separation of biotechnology-derived proteins. This research was to compare this new technology to the current methods of SDS polyacrylamide gel electrophoresis (SDS-PAGE) and high-performance size-exclusion chromatography (HPSEC). The molecular mass of four different recombinant proteins were determined by two commercialized SDS non-acrylamide gel-filled capillary columns, SDS-PAGE, and HPSEC. The data obtained showed that the SDS non-acrylamide gel-filled capillary columns were compatible with the SDS-PAGE technique for molecular mass determination. HPSEC was shown to be unreliable for molecular weight determination. SDS non-acrylamide gel-filled capillary …

Investigation Of Electron Transfer From Carbonylmetallate Anions To Electron Acceptors, Joseph Kofi Agyin

Masters Theses

This study investigated electron transfer potential of the carbonyl-metallate anions cyclopentadienylirondicarbonyl and methylcyclopentadienyliron-dicarbonyl anions to the electron acceptors 2,2-dinitropropane, 1,1-dinitrocyclohexane, $\alpha$,p-dinitrocumene, methyl cyclopentadienyl-mercury(II) chloride and iodide.

The findings from this study indicated that: (a) the expected products could not be obtained from reactions of the anions with the dinitro-substrates, and (b) the mercurials reacted with the anions but the expected products, (ferrocene and methylferrocene), was the minor product and an unexpected (methyl) cyclopentadienylirondicarbonylmercury(II)-chloride or iodide was the major product.

Synthesis Of Symmetric And "Mixed-Ligand" Homocyclopentadienyl Ruthenocenes, John Adjeiku Amanfu

Masters Theses

No abstract provided.

Computational Neural Networks In Chemistry: Model Free Mapping Devices For Predicting Chemical Reactivity From Molecular Structure, David Wayne Elrod

Dissertations

Computational neural networks (CNNs) are a computational paradigm inspired by the brain’s massively parallel network of highly interconnected neurons. The power of computational neural networks derives not so much from their ability to model the brain as from their ability to learn by example and to map highly complex, nonlinear functions, without the need to explicitly specify the functional relationship. Two central questions about CNNs were investigated in the context of predicting chemical reactions: (1) the mapping properties of neural networks and (2) the representation of chemical information for use in CNNs.

Chemical reactivity is here considered an example of …

Synthesis Of Organometallic Polymers, Po-Chang Chiang

Masters Theses

By the middle of the nineteenth century, organic chemists found high molecular weight compounds as by-products of some of their experiments. These compounds were thought of as products of a failed reaction. It was not until sixty years ago that the first polymers were deliberately synthesized. Today polymers are used in almost every facet of life and they are becoming more important with each passing day.

This research project focused on synthesizing conducting organometallic polymers. By linking aromatic rings with transition metals, the resultant polymers should have good electrical conductivity because of the interaction of (a) the p electrons on …

Single And Double Ionization Of Helium By Highly Charged Sulfur Ions, Karen M. Lifrieri

Masters Theses

Single and double ionization of helium by highly charged sulfur projectiles is investigated over an energy range of 0.16 to 1.6 MeV/u. Absolute cross sections for the processes of pure ionization, ionization associated with single capture, and ionization associated with single loss by S^6,13+ projectiles were experimentally determined and compared with previous results and theories. Ratios of double-tosingle ionization for each outgoing projectile charge state were also determined and compared with theory. The pure ionization ratios for S⁶⁺ at the highest energies investigated show the q²/E dependence predicted by Knudsen et al. (1984). For S^{13+ …}

Selected Studies On Certain Iron Sandwich Complexes, Mashitah M. Yusoff

Masters Theses

In these studies, the synthesis of [2.3](1,3)cyclopentadiendoparacyclophane was attempted. Like ferrocene and [2.2]paracyclophane, it is expected to exhibit transannular π-electronic interaction throughout its molecular structure and therefore, one dimensional semiconductivity.

The preparation of dialkylferrocenes had resulted in complex inseparable mixtures. Due to the fluxional nature of its intermediates, their conversion to stable Diels-Alder adducts would facilitate analysis. In this project, certain Diels-Alder adducts of bis-cyclopentadienyliron dicarbonyl intermediates were prepared for analysis.

Very few transition metal complexes of pyrrole are currently known. [2.2](2,5)Pyrroloparacyclophane was perceived to be stable especially as a part of an iron sandwich complex. The final phase …

Reductive Cleavage Of Cyclopentadienylmanganese Tricarbonyl, Mani S. Iyer

Masters Theses

Since the isolation of ferrocene in 1951, it has been shown to behave like benzene and may be acylated, sulfonated, metalated, and arylated. Like benzene, it also resists hydrogenation.

Daniel Trifan and Louis Nicholas (1957) were the first to show that ferrocene can be smoothly degraded by lithium and ethylamine. The isolation of free cyclopentadienyl ion on hydrolysis of the reaction mixture indicates that the cleavage leads initially to cyclopentadienyl lithium salt. A similar procedure applied to cyclopentadienylmanganese tricarbonyl also resulted in the formation of cyclopentadienyl lithium salt. This, when added to ferrous chloride, gave ferrocene. This technique can be …

Micellar Catalysis Of Hydrolysis Of Substituted Hydroxamic Acids With Perfluorooctanoic Acid, Zhongyuan He

Masters Theses

The work demonstrated the effects of differently located and substituted phenyl groups, as well as aliphatic groups in the hydroxamic acids, on micellar catalysis with perfluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution.

Kinetic rate constant-surfactant concentration profiles for the decano-, 2,5-dimethylphenylaceto-, 4-isopropylphenylaceto-, 4-phenylbutano-, and 6-phenyl-hexanohydroxamic acids were examined and analysis on the data obtained were reported.

The pseudo-phase ion exchange (PPIE) model has been satisfactorily applied to explain the observed micellar effects.

Further investigation into more appropriately substituted hydroxamic acids is suggested in order to obtain a more complete set of data and further evaluation.

Reactivities Of Some Aromatic Compounds At Supercritical Water Conditions, Chun-Cheng Tsao

Masters Theses

The goals of this study are the removal of nitrogen from the extraction products of coal by Supercritical Water and the development of an understanding of the reactions leading to this removal. Six model compounds with structures similar to the intermediates of the coal liquefaction processes were studied. Benzylamine generated toluene through hydrogen abstraction after the C-N bond rupture. To a lesser extent, the oxidation of the benzylic carbon took place leading to benzene formation. Both reaction pathways occurred with equal probability for benzylidenebenzylamine, producing comparable yields of benzene and toluene. Benzaldehyde generated benzene through the oxidation/decarboxylation sequence. Benzyl alcohol …

An Analysis Of Dissolved Organic Compounds And Their Contribution To Iron Complexation In The Shallow Leachate Plume Of The West Kl Landfill Kalamazoo, Michigan, Eric Fahle

Masters Theses

High concentrations of dissolved iron are present in downgradient groundwater samples adjacent to the western border of the West KL Landfill. Analysis by Rudder (1988) of groundwater samples indicates oversaturation of selected iron oxides, iron sulfides and siderite in monitoring wells TW-4 and M3.

Previous research suggests that pyrogallol, gallic acid, tannic acid and similar organic compounds may retard the oxidation of ferrous iron in the shallow leachate plume of the West KL landfill (Rudder, 1988). Present research utilizing solid phase extraction, reverse phase high performance chromatography, Fourier transform IR spectrophotometry, UV/Visible spectrophotometry, and gas chromatography/mass spectroscopy indicate that pyrogallol, …

Intracellular Degradation Of Ribosomes In A Mesophilic And A Thermophilic Species Of Bacillus, Joe William Davis

Dissertations

The rates of intracellular degradation of ribosomal proteins were compared in a mesophilic and a thermophilic species of Bacillus. Cells were grown under various incubation conditions in the presence of a 14^C-protein hydrolysate m order to label the ribosomes. Rates of ribosome degradation were evaluated in terms of changes in the specific activity of in vivo ribosomes as a function of incubation time. The results indicated that, under most conditions, ribosomes were degraded (in vivo) at similar rates in both the mesophile and the thermophile. In some studies, ribosome degradation rates were slightly faster for the thermophile than for the …

Kinetics Of The Metal-Exchange Reaction Between Ortho-Phospho-Dl -Serinenickelate(Ii) And Copper(Ii), Jeffrey M. Peterman

Masters Theses

No abstract provided.

Micellar Catalyzed Hydrolysis Of Hydroxamic Acids By Perfluorooctanoic Acid, Mohammad Hashem Akhavan Tafti

Masters Theses

The work reported herein demonstrated that a perfluorocarboxylic acid does indeed behave as a reactive counterion surfactant exhibiting micellar catalysis, this conclusion was further verified by subsequent experimentation.

Rates of acidic hydrolysis of octano-, phenylaceto-, and 4-bromo phenylacetohydroxamic acid have been determined in aqueous perfluorooctanoic acid--a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolysis of octanohydroxamic acid but not for the arylacetohydroxamic acids.

Further investigation into finding a more water soluble surfactant which has reactive counter ions is suggested in order to test the theoretical equation (based on the pseudo phase model) appropriate for this surfactant …

Synthesis Of N And C Nucleosides Via Cycloaddition Reactions A New Approach To An Old Problem, Glenn L. Heise

Dissertations

No abstract provided.

Synthesis And Study Of Novel Quinoxaline Di-N-Oxide And 3-Acyl-2-Methylquinoxaline Di-N-Oxides, Cyprian Okwara Ogbu

Masters Theses

This research project consists of two parts. The first involved the synthesis of a novel quininoxaline di-N-oxide via benzofuroxan. The second part was the use of this compound as a synthetic precursor.

It was assumed that 3,4-dimethylaniline would be successfully converted to 5,6-dimethybenzofurazan 1-oxide (5,6-dimethybenzofuroxan) through a sequence of reaction steps. Fortunately, this assumption was correct as the desired compound was produced. This compound was utilized in synthesizing the novel 3-acetyl-2,6,7-trimethylquinoxaline 1,4-dioxide. From the structure of this adduct, it is believed that it will take part in condensation reactions associated with methyl ketones without disrupting the quinoxaline di-N-oxide framework, and …

Synthesis And Reactions Of A-Diketones And Preparation Of Some New Benzimidazoles, Mohamad Reza Agharahimi

Masters Theses

This report will discuss the synthesis of 2,5-dl-(p-chlorophenyl)-3,4-dioxoadiponitrile and its reactions. This compound exists in the form of 4,4'- dichloropulvinic nitrile which is a precursor to 4,4'-dichk>rovulpinic acid. These compounds have been shown to have antiinflammatory activity in rats.

The benzimidazole and pyridazine derivatives of 4,4'-dichioropulvinic nitrile and the benzimidazole derivative of 4,4'-dichk>rovuipinic acid are another group of compounds that are also believed to have useful biological activities. The Pinner synthesis of imidates is used to make the intermediate to the benzimidazole derivative of 4,4'-dichloropulvinic nitrile.

This report will include the methodology of the reactions and …

A Synthetic Approach To Novel Heterocyclic Herbicides, Paul Antony Pathadan

Masters Theses

The purpose of this research study was to prepare novel heterocyclic herbicides. The first phase of the project was to synthesize 1-(nitromethyl)-4-phthalazone.

In the second phase 1 - (nitromethyl)-4-phthalazone was treated with 1,3-propane-dithio-di-p-toluene sulfonate in presence of sodium hydride to get the target compound 4-(1'-nitro-l,3-dithiane)phthalazone.

It is believed that this compound might block the electron transport system of aerobic cells¹ . So further investigation of this compound may lead to novel herbicides.

Kinetics Of The Metal-Exchange Reaction Between N-(2-Pyridylmethyl)Iminodiacetatonickel(N) And Copper(Ii), Kassahun W. Beyene

Masters Theses

The reaction between N-(2-pyridylmethyl)iminodiacetatonickel(II) and copper(II) was studied spectrophotometrically between pH 2.30 and 3.30 over a 10-fold variation in copper concentration at an ionic strength of 1.25M, and a temperature of 25.0+0.1^oC. The reaction is first order in both NiPyIDA and copper(II). Terms involving proton attack and a copper dependent dissociation of the nickel complex were resolved from the data. Evidence is given for a stepwise unwrapping mechanism PyIDA from the nickel complex, followed by copper attack to give a dinuclear intermediate. A general mechanism is presented which is consistent with the kinetic data.

Comparisons to analogous nickel-aliphatic …

Effect Of Polymerization Conversion On The Experimental Determination Of Monomer Reactivity Ratios In Copolymerization, Sevim Zeynep Erhan

Dissertations

In this study the comparison of the methods used to calculate monomer reactivity ratios from experimental copolymer composition data is targeted.

For this purpose, nine samples of each of nine different concentrations of styrene-methyl methacrylate monomer mixtures were prepared. These mixtures were then polymerized for different times ranging from one to nine hours and the percent conversion to copolymer was determined.

The compositions of these copolymers were determined by their refractive index increments measured in two different solvents. Ultraviolet absorption spectroscopy was also studied as a possible method to find copolymer compositions. Though this method has been used previously, UV …

Investigation Of The Synthesis And Polymerization Behavior Of Vinyl Benzoate, Selim Mehmet Erhan

Dissertations

The goal of this study is to present a method that gives higher conversions and molecular weights for the polymerization of vinyl benzoate than obtained in previous investigations.

Polyvinyl benzoate has benzene rings attached to the backbone chain, therefore is hard and rigid. This is a characteristic which has a large application area. However previous studies in polymerizing vinyl benzoate with bulk and solution polymerizations reported low yields and troublesome crosslinking, which has limited its application. Emulsion polymerization method has the advantage of giving high polymerization rates together with high molecular weights, and therefore was chosen as the method for …

The Preparation And Reaction Of Novel Glycosyl Ureas And Thioureas, Robert Scott Johnson

Masters Theses

No abstract provided.

High Performance Liquid Chromatographic Determination Of Thromboxane B2 In Human Serum As A Methoxime-Panacyl Ester Derivative, Robert H. Pullen

Masters Theses

No abstract provided.

Reactive Counterion Surfactant Catalysis Of Hydroxamic Acid Hydrolysis With Perfluorooctanoic Acid, Mohamed El-Sayed Ayoub

Masters Theses

A micellar effect upon the rate of hydrolysis of hydroxamic acids in aqueous perfluorooctanoic acid has been demonstrated for hydroxamic acids with chain lengths of six , eight, and ten carbons. In this system the counterion, hydrogenion, is a catalyst. Typical rate constant-surfactant concentration profiles for micellar catalysis were obtained. The results for these hydrolyses are consistent with the pseudo-phase model for micellar effects.

In addition the Arrhenius activation energies were determined for the reaction of octanohydroxamic acid at surfactant concentrations above and below the critical micelle concentration of the surfactant. The activation energy is lower for reaction in the …

Simultaneous Knudsen- And Torsion-Effusion Measurements Of The Vapor Pressures Of Triphenyl Aluminum And Triphenyl Boron, Steven Wayne Govorchin

Masters Theses

The sublimation pressures of triphenyl aluminum and triphenyl boron have been determined from simultaneous measurements of the rate of mass effusion and torsional recoil. For triphenyl aluminum the measured vapor presures are expressed by the equations:

logio (P_k/P°) = (12.76 ± 1.25) - (8214 ± 572) (K/T)

logio (P_t/p °) = (12.83 ± 1.34) - (8206 ± 615) (K/T)

where P_k and P_t are the pressures measured by the Knudsen-effusion and torsional-recoil techniques, respectively, and p° = 101.325 kP_a. For triphenyl boron the measured vapor pressures are expressed by the equations:

log …

The Design And Construction Of Microprocessor-Computer Controlled Rapid Scanning Fiberoptic Spectrophotometer, Kathleen Marie Tobin

Masters Theses

Conventional spectrophometers require the transfer of a sample to a cuvette for obtaining spectra. The measurement of absorbance in situ can be accomplished using a fiber optic probe which can be placed directly in the sample. The fiber optic probe also minimizes environmental factors such as thermal or vibrational which may affect the absorbing species. A rapid scanning speed allows for essentially simultaneous wavelength monitoring.

The effect of coupling a rapid scanning spectrophotometer with a fiber optic probe provides for an extremely versatile system. When used in comjunction with a microprocessor or computer, this approach offers advantages such as data …

Reactions Of Supercritical Water With Quinoline And Related Compounds, Zhuangjie Li

Masters Theses

One function which coal processing can perform is the removal of heteroatoms to yield a less polluting product. The removal of nitrogen atoms from the model compounds quinoline and aniline, which are believed to be representative of the nitrogen functional groups found in coal, was studied using supercritical water (SW) as the fluid. Water at these conditions serves as a reactant, helping to promote the rupture of the heterocyclic ring and in the removal of nitrogen attached to an aromatic ring. Heterocyclic ring rupture leads to the formation of several methylated products, methyl and dimethyl anilines, phenols and quinolines. The …

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise

Masters Theses

Experiment 1: The reaction of various glutaconaldehyde salts (Na⁺ or K⁺) with glycosyl isothiocyanates has resulted in the formation of a novel class of compounds. Relatively mild conditions were utilized for the synthesis which occurs in four steps, and in good yield, starting from glucpseptentaacetate. These reactions were found to be regiospecific. The unique physical and spectral properties of the model compound 1-(2,3,4,6-tetra-0-acetyl-β-D-glycopranosyl)-2-thiono-3-pyridine carboxaldehyde are also discussed.

Experiement 2: Early synthetic methodologies have recently been utilized in the synthesis of 4-aryl-2-oxytetronimides. These compounds have been found to participate in condensation reactions with various substituted o-phenylene diamines. A …

Cobalt (Iii) Complexes With (R) - 1, 2-Diaminopropane And Its Derivatives, Christopher John Rudy

Masters Theses

(R)-1, 2-Diethylaminopropane (N,N' -Etlpn) was prepared by LialH₄ reduction of (R)-1-2-diacetamidopropane (m.p. 153.5°C). The [∝]_D of N, N'-Melpn and N,N'-Etlpn was related to that of 1pn and was concentration dependent. (R)-1, 2-Dibenzylaminopropane was prepared. Complexes of trans, trans- and trans, cis-dinitrobis ((R)- 1, 2-diethylaminopropane) cobalt (III) were perpared. The hexadecadal rule was used to help assign the nitro oxygens of the complexes to sectors adjacent to the axial amine hydrogens and within the boundaries of the λ- chelate rings. The CD spectra was solvent dependent. The instability of trans-[Co (III)N₄X₂]⁺ complexes was related …

The Survival Of Mesophilic And Thermophilic Bacteria Subjected To Uv Irradiation, Sajida A. Shaikh

Masters Theses

Survival curves were determined for the mesophile, Bacillus licheniformis and the thermophile, Bacillus stearothermophilus after subjecting the cells to ultraviolet irradiation. Cells were grown at 37°C for the mesophile and at 55°C for the thermophile.

At low UV exposure times, the thermophile was more resistant to UV irradiation (had a better survival rate) than was the case for the mesophile. At higher exposure times, the situation was reversed, the mesophile having a greater survival rate than the thermophile.

The effect of changes in the temperature during irradiation was also determined. Thermophiles were greatly affected by changes in temperature while the …