Physical Sciences and Mathematics Commons^™

Kinetics Of Ternary Complex Formation Reactions Of The Nickel(Ii) Complexes Of Ethylenediaminediacetate And Triethylenetetramine With Bidentate Donors, Lawrence H. Kolopajlo

Dissertations

The stopped-flow technique was used to measure rate constants for ternary complex formation involving both NiEDDA and Ni(trien)('2+), and bidentate donors. The reactions of both NiEDDA and Ni(trien)('2+) with bipy, phen, en, and sar were studied. In addition the reaction of NiEDDA and gly was studied. The reactions were of the first-order with respect to either nickel complex, and with respect to enH('+), bipy, and phen. The reactions involving phen and bipy were independent of pH and were reversible. The formation rate constants for the systems containing diamine reactants are as follows:

(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)

For …

Determination Of Organophosphorus Compounds By Hplc With Post-Column Photochemical Degradation Followed By The Formation Of Reduced Heieropolymolybdate, Stephen R. Priebe

Dissertations

A novel method for the determination of organophosphorus (OP) compounds by HPLC with post-column photochemical and chemical derivatization reactions has been developed. The OP compounds eluted from the column were photochemically degraded to orthophosphate by the use of a 450 W xenon lamp in conjunction with an auxiliary photodegradation reagent. The photodegradation reaction was studied extensively by means of batch irradiations with triethylphosphate as a model compound. The effects of the initial concentrations of triethylphosphate and ammonium peroxydisulfate, and of varying the pH of the reaction medium were determined. A survey of potential interferences was performed. Copper(II) ion was found …

Separation Of Piperylene Concentrate Via Metathesis Catalysis, Donald R. Allred

Retrospective Theses and Dissertations

Diolefin metathesis, using a Re2O7 catalyst, failed to show a reactivity difference due to conjugation of double bonds. However, the same system allows reaction of pentadiene while not affecting cyclopentene yielding a successful reaction ΓÇô separation scheme for a piperylene concentrate mixture.

Isolation And Characterization Of The Serum Ferroxidase Inhibitor, Melissa Page Calisch

Master's Theses

strong evidence suggests that the serum ferroxidases (ceruloplasmin andferroxidase II) promote the formation of Fe-III transferrin and thereby stimulate the turnover of iron from tissue stores. Ceruloplasmin is the major ferroxidase in human serum; whereas, ferroxidase II accotmts for an increased proportion of the activity in less highly developed animals. A large fold increase in total ferroxidase II activity was observed when both human and rabbit sera were subjected to gel-filtration on sephadex G-200. This indicated that whole serum might contain a potent inhibitor of ferroxidase II. Such an inhibitor has been isolated and purified to homogeneity by a combination …

Micellarly Catalyzed Reaction Of Substituted Benzohydroxamic Acids, Nop Utrapiromsuk

Dissertations

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the …

Analysis Of Organic N-Chloramines In Chlorinated Drinking Water, John Po Wen Yang

Chemistry & Biochemistry Theses & Dissertations

This thesis describes the development of a sensitive method for the separation and quantitation of organic N-chloramines in chlorinated tap water. 5-Dimethylaminonaphthalene- l-sulfinic acid has been synthesized and characterized. It yields highly fluorescent dansyl derivatives on reaction with N-chloramines. Conditions of the derivatization were optimized for the detection of N-chloropiperidine at concentrations in aqueous solution of 10^-7 M. The technique gives a quantity of derivative which is proportional to the concentration of chloramine present over the range examined (10^-7 M to 10^-4 M). High pressure liquid chromatographic separation of dansyl derivatives of amines and amino acids has …

Flash Photolysis: The Technique And Its Application, Marabeth G. Soltis

Honors Theses

The application of flash photolysis in photochemistry offers an effective means to directly investigate reactive intermediates. This powerful technique rapidly converts a high percentage of molecules in their ground electronic state to upper excited states. This enables the disappearance of the excited species to be observed and kinetic information concerning the rate law and rate constants to be measured. The purpose of our work is to investigate the kinetics of the rate of decay of triplet anthracene in dilute solutions and to obtain rate constants for this reaction. The reduced expression for the decay of triplet anthracene is written: -dT/ …

The Gas Phase Ozonolysis Of Tetramethylethylene, Catherine A. Rusik

Honors Theses

The gas phase reaction between ozone and olefins is thought to proceed via an oxy-peroxy biradical intermediate, which may undergo cleavage or a variety of hydrogen abstractions. The validity of this biradical mechanism is investigated in a study of the products and stoichiometry of the gas phase ozonolysis of tetramethylethylene. Various pathways in the ozonolysis mechanism for this olefin are compared thermochemically to assess the relative favorability of the reaction possibilities of the biradical intermediate. Experimentally, olefin-rich and ozone rich reaction conditions are studied in the concentration range 10-800 ppm, using gas chromatography. The concentration of ozone present is determined …

Liquid Chromatographic Studies Of Polar Aromatic Compounds In Soil, Jonathan Stuart Green

Honors Theses

The purpose of this project is to identify a component or components in red pine tree soil which may be associated with fungus growth inhibition.

Microcomputer Interfacing With Chemical Instrumentation, Joel R. Meyer

Honors Theses

In this paper we discuss the interface of a liquid chromatograph with an· Apple II+ microcomputer, The system consists of a Varian 5000 High Performance Liquid Chromatograph (HPLC), a Tracor 970A variable wavelength absorption detector (VWD), an Apple II+ computer, and an interface unit which consists of an operational amplifier and a Mountain Computer A/D + D/A converter. The op. amp. modifies the output signal of the VWD (0 to +lV) to meet the input specifications of the A/D converter (-5V to +5V). This allows the conversion of the continuous analog signal from the VWD to a digital signal, which …

Trace Analysis Of Uranium By Laser Induced Fluorescence Excitation ( Life ), R. Kenneth Marcus

Theses & Honors Papers

No abstract provided.

Synthesis Of Potential Insecticides And New Synthetic Applications Of Vinamidinium And Azavinamidinium Salts: Reactions With Reducing Agents And Nitro Compounds, Michael J. Lizzi

Retrospective Theses and Dissertations

This report discusses the research conducted in two areas: the synthesis of potential insecticides and the investigation of vinamidinium and azavinamidinium salt chemistry. Firstly, four classes of compounds were synthesized and characterized in the investigation of new potential insecticides. These classes of compounds include a-formamidine methyl esters, amidines, diacylhydrazines and 2,5-disubstituted-1,3,4-oxadiazoles and were characterized via NMR and infrared spectroscopy. This account also reveals and discusses the experimental conditions and procedures necessary for the preparation of these potential insecticides. Secondly, the reaction of [ 3-(dimethyl amino)-2-azaprop-2-en-1-ylidene] dimethyl ammonium chloride (Gold's Reagent) with nucleophiles such as activated (nitro) methylene compounds was examined …

The Temporal And Spatial Distribution Of Hydrocarbons In Atmospheric Deposition From Stations Surrounding Lower Chesapeake Bay, David Benjamin Webber

OES Theses and Dissertations

Hydrocarbon concentrations were determined in bulk, wet, and dry deposition samples from urban and non-urban locations surrounding lower Chesapeake Bay. Mean hydrocarbon concentrations in bulk deposition samples were over three times greater at the urban station indicating a localized source. The major hydrocarbons present were n-alkanes, polycyclic aromatic hydrocarbons (PAH), and the unresolved complex mixture (UCM). The PAH and the UCM were an indication of significant anthropogenic inputs while the odd/even distribution of the n-alkanes was an indication of biogenic sources. These findings indicated seasonal trends of highest biogenic hydrocarbon inputs in the spring and summer months and highest anthropogenic …

The Regioselective 3-Alkylation Of Piperidine, Richard Dunn Todd

Chemistry & Biochemistry Theses & Dissertations

The compounds: 3-allylpiperidine, 3-ethylpiperidine and 3-n-butylpiperidine have been synthesized by regioselectively alkylating the three position of piperidine. Piperidine was converted to N-chloropiperidine and then dehydrohalogenated to produce Δ¹-piperideine. The enamide anion was generated by adding solutions of Δ¹-piperideine to ethylmagnesium bromide or lithium diisopropylamide. Addition of alkylhalides produced 3-alkyl- Δ¹-piperideine which could be reduced or alkyllithiated to give 3-alkylpiperidines or 2,3-dialkylpiperidines respectively.

The yields of products were low and the reaction generated a continuum of mono- and di-alkylpiperidines and there was evidence that several dimeric piperideines were formed. The low yields were discussed in …

Ortho Cyclization Reactions Of Catecholamines, Robert Lee Hudkins

Chemistry & Biochemistry Theses & Dissertations

A study was undertaken to examine the potential for ortho cyclization associated with the synthesis of 1,2,3,4,-tetrahydroisoquinolines using the Pictet-Spengler reaction. Specif1cally, the condensation of the biogenic amines, dopamine, norepinephrine and epinephrine were carefully examined in light of current literature and the facility and extent of ortho cyclization in each case. The para isomers of these three biogenic amine condensation products were isolated and characterized, while only the ortho isomer derived from dopamine was found stable and could be isolated, and structurally identified. These studies demonstrate that a second cyclization product does, in fact, form in each instance and that …

Synthesis And Evaluation Of Polymeric Ether Glycol Derivatives For Use As Transducer Fluids, Cynthia K. Mccurry

Retrospective Theses and Dissertations

A series of end-capped PAG (n-butyl, n-alkyl substituted polypropylene glycol) and PPGs (bis-di-alkyl-,bis-di-halo-, bis-di-fluoroalkylpolypropylene glycol) were synthesized. Optimum reaction conditions were determined in regard to time, temperature, reaction ratios, and solvents for each of the PAG and PPG derivatives. An investigation of the named PAG and PPG derivatives as potentially new sonar transducer fluids was carried out. Density, viscosity and sound speed measurements with regard to temperature, as well as water solubility measurements, were carried out for several of these derivatives. The desirable properties possessed by several of these derivatives make them of potential value in application as transducer fill-fluids.

Flow Injection Atomic Absorption Assay Of Copper And Zinc In The Plasma Of Age Dependent Audiogenic Seizure Susceptible Mice, Neal Dwain Byington

University of the Pacific Theses and Dissertations

Flow injection atomic absorption procedures with less than 10%RSD at 1.0 ppm were developed for the assay of copper and zinc in 10 μL samples of mouse plasma. The flow injection apparatus was designed with a pulseless liquid flow control system, regulated by inert gas pressure. The aspiration liquid is 6% t-butanol in water. After exhaustive parameter optimizations, copper assays were conducted with the conventional air-acetylene flame at 324.754 nm and zinc assays were conducted with the unconventional argon-hydrogen air diffusion flame at 213.856 nm. The argon-hydrogen flame system was chosen because it absorbs very little ultraviolet light.

The developed …

Electrochemical Determination Of The Heterogeneous Electron Transfer Kinetics Of Soluble Spinach Ferredoxin, Charlene D. Crawley

Theses and Dissertations

The application of electrochemical techniques to biological systems has become an attractive method for characterizing the redox and electron transfer behavior of biomacromolecules. This study focuses on the role of soluble spinach ferredoxin (Fd) in photosynthesis where it functions as an electron carrier to membrane bound species in the plant chloroplast. An electrochemical model is used where in Fd now serves as a soluble redox species which undergoes oxidation and reduction via electron transfer at an electrode. This type of model is significant in that both the membrane and electrode reactive sites are characterized by charged bilayer interfacial regions which …

Controlling The Number Of Metal Sites To Which A Poly(Tertiary Phosphine) Coordinates To Group 6 Metal Carbonyls, Nestor Paul Hansen

Masters Theses

The compounds trisdiphenylphosphine(tricarbonyl) metal and trisdiphenylvinylphosphine(tricarbonyl) metal of molybdenum and tungsten were prepared. These compounds were allowed to react with diphenylvinylphosphine and diphenylphosphine, respectively, in the presence of azobis(2-methyipropio)nitrile or potassium t-butoxide to yield the complex containing bis(diphenylphosphino) ethane as a chelated ligand.

The tris-substituted compounds showed a large degree of lability which prevented the isolation of the desired, (OC)₃M(Ph₂PCH₂CH₂PPh₂)₃, compound which contains three ditertiary phosphines acting as monodentate ligands.

Coordinated diphenylphosphine and diphenylvinylphosphine pentacarbonyl compounds of chromium, molybdenum and tungsten were prepared and allowed to react in …

A Comparison Of The Surface Polysaccharides Of Rhizobium Trifolii Su843 With Its Genetically Altered Mutant, 8002, Which Is Defective At Root Hair Curling (Hac-), Elroy Alfredo Turnbull

Masters Theses

Bacteria of the genus Rhizobium are capable of forming a complex nitrogen fixing (fix⁺) symbiotic association with leguminous plants. The surface polysaccharides are believed to be essential in the symbiotic process. The surface polysaccharides of a genetically altered Rhizobium trifolii mutant, 8002--which does not cause root hair curling (HAC^-), forms no nodules (Nod^-) nor fixes nitrogen (Fix^-)--is compared with its parent, SU843, which causes root hair curling (HAC⁺), forms nodules (Nod⁺), and fixes nitrogen (Fix⁺). Three types of surface polysaccharides--extracellular polysaccharide(s) (EPS), capsular polysaccharide(s) (CPS), and …

The Reaction Of 4-Vinylcyclohexene With Palladium (Ii), Kathy Ellen Beeler

University of the Pacific Theses and Dissertations

This program of study was concerned with the elucidation of the causes(s) behind the inability of various workers to reproduce the work of Fyre and Kuljian on the rearrangement of 4-vinylcyclohexene to 1,5-cyclooctadiene by the action of palladium (II).

A Spectroscopic Study Of Intramicellar Environment With Merocyanine Dye Probes, Elise Jane Daggs

University of the Pacific Theses and Dissertations

The effects of micelle forming surfactants hexadecyltrimethylammonium bromide, sodium dodecyl sulfate and igepal CA~6JO on the visible spectra of merocyanine dyes of the form 1-alkyl-4-[(3', 5'-alkyl oxocyclohexadienylidene)ethylidene]- 1,4-dihydropyridine were studied. In all cases the visible spectrum shifted to the red when the dye was incorporated into the micelles. The magnitude of the shifts was found to be dependent on the substituted groups and the positioning of the chromophore of the dye in the micelle aggregates. The shifts indicate a highly hydrated environment about the surfactant head groups and an environment equivalent to that of pure ethanol solvent at some undetermined …

Interfacial Electrochemistry Of Cytochrome C And Myoglobin, Edmond F. Bowden

Theses and Dissertations

The interfacial electrochemistry of horse heart cytochrome c was studied at metal and metal oxide electrodes. Sperm whale myoglobin reactions at metal oxide and surface modified electrodes were also investigated. Emphasis was on the measurement and mechanistic interpretation of the heterogeneous electron transfer kinetic parameters for these electrode reactions.

The motivation for this study stems from the fact that some electron transfer proteins, e.g., cytochrome c, transfer electrons heterogeneously in physiological systems. Specific electrodes may, therefore, serve as suitable models for physiological surfaces. Electrode and membrane interfaces are both electrically charged and both have oriented hydration water layers.

The cyclic …

The Interaction Of R. Leguminosarum 128c53 With Pea Root Proteins And A Comparison Of The Surface Polysaccharide With A Mutant Defective In Nodulation, Ru-Po Lee

Masters Theses

The Rhizobium extracellular polysaccharides (EPS) and lipopolysaccharides (LPS) are implicated in the symbiotic process. The interaction between host root protein fractions and symbiont EPS-polyacrylamide affinity support has been investigated. Ten percent root protein fractions had been observed to bind to the affinity support. The compositions of the polysaccharides from the parent R. leguminosarum and its Exo^-1 mutant have also been compared. The Exo^-1 mutant produces diminished amount of EPS and does not nodulate the host pea roots. Five kinds of polysaccharides from the parent were obtained: EPS, capsule polysaccharides (CPS I) washed from the bacteria with saline solution, …

An Investigation Of Cadmium And Sulfur Reactions In Dimethylsulfoxide, Howard W. Hogle

Dissertations and Theses

The study of the reaction of cadmium and sulfur in dimethylsulfoxide (DMSO) is presented. Specifically, the reaction of dissolved molecular sulfur in DMSO at temperatures greater than 90°C with freshly precipitated metallic cadmium is followed by UV-visible spectrometry, atomic absorption spectrometry, and Raman spectrometry. Evidence for the formation of a new cadmium-sulfur species and S₃- is discussed. In a second reaction, an equilibrium sodium polysulfide solution in DMSO is titrated with a solution of cadmium ion at room temperature and the reaction progress is followed by means of UV-visible spectrometry. A calculation of the average number of polysulfide …

A Laser Interferometric Study Of Electric Field Effects On Methane-Oxygen Flame Plasmas, Mark D. Prairie

Masters Theses

A laser interferometer is developed to study the refractive index field, aerodynamic structure, and three dimensional temperature profile of a methane-oxygen flame system under the influence of D.C. electric fields. A combined graphical-numerical method is used to transform the observed interference patterns into radial temperature distributions. The results indicate that the electric field exerts a marked influence on the flame stability, geometry, and charged particle flow. Experimental evidence shows that these effects are most apparent under fuel rich conditions. It is suggested an electric field may change the concentration gradients of reacting species, leading to an altered course of fuel …

Cleavage And Deoxygenation Of Phenolic Ethers, Derhsing Luu

Masters Theses

Dibromotriphenylphosphorane (DTP) in acetonitrile at 50°C was found to cleave ß-naphthylmethyl phenyl ether in preference to ß-naphthyl benzyl ether, 62% and 30% cleavage, respectively. Reaction of ß-naphthyl benzyl ether in dichloromethane at reflux produced 67% cleavage.

The quasiphosphonium complexes obtained by reaction of phenolic compounds with DTP were found to be reduced by several reducing reagents to give the corresponding aromatic hydrocarbons. Reaction of p-cresol with DTP, followed by lithium aluminum hydride reduction gave 38% toluene; sodium naphthalide reduction in THF gave 32% toluene; sodium in liquid ammonia reduction gave 12% toluene; sodium naphthalide reduction in DMF gave 15% toluene. …

A Comparison Of The Surface Polysaccharides From Rhizobium Japonicum Strains I110ars And 61a76str, And The Isolation Of Soybean Root Proteins Responsible For The Binding Of Eps From R. Japonicum Strain I110ars, Richard F. Koehler

Masters Theses

The surface polysaccharides of Rhizobium are implicated in the symbiotic process. The composition of the surface polysaccharides from two strains of Rhizobium japonicum, I110 ARS and 61A76 str, have been compared. Five polysaccharide fractions are obtained from the I110 ARS strain. They are the EPS (extracellular polysaccharide), CPS-1 and CPS-2 (capsular polysaccharide fractions), LPS (lipopolysaccharide) and Phe (polysaccharide found in the phenol layer from the phenol/water extraction). These polysaccharide fractions have identical sugar compositions. Four polysaccharide fractions are obtained from the 61A76 str strain. These are the EPS, CPS-1, SmPS (small molecular weight polysaccharide), and Phe. Each of these …

The Preparation Of The Coordination Compounds Of Palladium (Ii) And Spermine And Spermidine, Wenli Grace Lee

University of the Pacific Theses and Dissertations

The purpose of this study was to prepare and characterize complexes produced by the reactions of spermine and spermidine with palladium(II) chloride. A first analysis of the problem seemed to indicate that preparation of the complexes should be straightforward and not difficult. Bonding of the nitrogen atoms to the metals allows sterically for formation of two six-membered rings separated by a tetramethylene chain in a spermine complex, and by a six-membered chelate ring in a spermidine complex.

Hydroxide Binding Equilibrium In Hemerythrin, John David Mccallum

Dissertations and Theses

The measurement of the equilibrium constant and the thermodynamic parameters of the binding of hydroxide ions to the active site of hemerythrin, an invertebrate iron containing protein, was done by a new difference spectroscopic method. The method enables accurate measurements of equilibrium constants without accurate knowledge of molar absorptivities or protein concentrations and is novel in that it takes the difference between the two equilibrium mixtures, thus enabling the measurement of equilibrium constants when it is not convenient or possible to produce either substance as a pure reference material.