Chemistry Commons^™

Kinematics And Thermodynamics Of Nickel(Ii)-Glycine Complexes Using Carbon Magnetic Resonance, Donald Frederick Shepard

Chemistry and Chemical Biology ETDs

1-¹³C glycine was studied in nickel(II) solutions using carbon magnetic resonance (CMR). The carboxy bound nickel(II)-glycine complex and the kinetics of complexation between aquated nickel(II) ion and aquated glycine are described. It has been hypothesized that solutions containing no complexation higher than the chelated mono nickel(II)-glycine complex contain five magnetically different glycine species. The effects of these five magnetically different glycine species on the CMR spectra of the nickel(II)-glycine solutions are discussed. The lifetime of the carboxy bound complex is 7.87 x 10^-4 sec at 272 K with an activation energy of 9.74 kcal/mole, an activation enthalpy …

Synthesis Of Benzo[A]Pyrene And Derivatives: Labelling Of Positions 1, 2, 3, 11 And 12, Richard S. Bodine

Chemistry and Chemical Biology ETDs

The ketone, 3, 4-dihydrobenz[a]anthracen-1(2H)-one (1), was prepared in three steps from anthracene. Condensation of the lithioenolate of ethyl acetate with the ketone(1) in tetrahydrofuran at -78°C afforded ethyl (1-hydroxy-1, 2, 3, 4-tetrahydrobenz[a]anthracen-1-yl)acetate (2). Dehydration and dehydrogenation over palladium/charcoal provided ethyl (benz[a]anthracen-1-yl)acetate (3). Reduction of the ester (3) with diisobutylaluminum hydride in toluene at -75°C gave benz[a]anthracen-1-ylacetaldehyde (4) which was cyclized with methanesulfonic acid to benzo[a]pyrene (5). Saponification of the ester (3) gave benz[a]anthracen-1-ylacetic acid (6) which was cyclized with methanesulfonic acid to benzo[a]pyren-11-o1 (7). Oxidation of the phenol (7) with Fremy's salt afforded the quinone, 11, 12-dihydrobenzo[a]pyrene-11, 12-dione (8). Reduction …

The Electrogenerated Chemiluminescence Of Trans-Stilbene Derivatives, James R. Wilson

Chemistry and Chemical Biology ETDs

A group of 15 compounds, all structurally related to trans­stilbene have been studied in systems of electrogenerated chemiluminescence (ECL). The compounds are substituted 2-phenyl indenes, dihydronapthalenes, and dihydrophenanthrenes. Absorption and fluorescence spectra, fluorescence quantum yield, cyclic voltammetry, and ECL were obtained for each compound. The ECL experiments were set up as single and mixed systems which used tri­para-tolylamine as the source of cation radicals. Each mixed system was studied in two different solvents, which were acetonitrile and a 1:1 mixture of acetonitrile and benzene. Single systems were studied only in the acetonitrile-benzene solution. Emissions at wavelengths longer than the fluorescence …

Chemiluminescence Studies Of Silicon Fluoride And Uranium Oxide, Russell A. Armstrong

Chemistry and Chemical Biology ETDs

Spectroscopic studies of the reactions of fluorine with silicon, silane and deuterated silane, and of oxygen with uranium are reported. Chemiluminescence and atomic absorption techniques have been employed to determine the kinetics, photon yields and branching ratios of the chemistry leading to the excited states of the radical SiF. The reaction of silicon vapor with fluorine occurs at nearly a gas kinetic rate (k₂=1.3 x 10^-10 cc molecule^-1 sec^-1). The overall system photon yield from the reaction of silane and fluorine to produce SiF(A➔X) and SiF(a➔X) emission were 5 x 10^-2% and …

Comparative Enzymology Of Glyoxalase I, Christina Margaret Schimandle

Chemistry and Chemical Biology ETDs

The role of the metal ion in rat erythrocyte glyoxalase I was evaluated. The apoenzyme was formed by dialysis against an EDTA-imidazole buffer. Fluorescence studies of the Mg⁺⁺- and Mn⁺⁺-dansylated glyoxalase I's suggest that the metal ion is near the active site of the enzyme and participates in the catalytic reaction. Stereochemical studies of the conversion of methylglyoxal to S-lactoylglutathione with Mg⁺⁺, Mn⁺⁺, Co⁺⁺ and Ni⁺⁺-glyoxalase I's show that the 0-lactate of S-lactoylglutathione (97±1.5%) is formed. This result suggests that the reaction mechanism is the same with a change …

In Situ Intercalation Of Tas2 In The Electron Microscope, G. Tatlock, Juana Acrivos

Faculty Publications, Chemistry

Electron diffraction had been used to study the formation of a variety of complex superlattices in the 1T, 2H and 4Hb polytypes of TaS2 during intercalation with hydrazine gas (N2H4), in situ in the electron microscope. Results are presented over the temperature range 15K-360K and are interpreted in terms of scattering from periodic lattice distortions linked to charge density waves. Comparisons are also made with similar effects in both the as-grown crystals and the TaS2 samples containing other adducts.

Physical Studies Of Hg(Ii) And Ag(I) Dna Complexes, Dawen Ding

Chemistry and Chemical Biology ETDs

The binding of Hg(II) and Ag(I) to the bases of DNA and polynucleotides induces strong absorption and CD bands. From electric dichroism studies, the transition moment of the difference absorption band at 293 nm is in the plane of the bases and has a huge negative CD band at 285 nm; while the corresponding 293 nm difference absorption band of DNA-Ag(I) complex is relatively CD inactive. A second band at 270 nm in the difference absorption spectrum of the DNA-Ag(I) complex has a large associated CD band at 270 nm. This transition is out of the plane of the bases. …

Synthesis And Studies Of A Carbon-13 Labelled Chemical Carcinogen, Robert E. Royer

Chemistry and Chemical Biology ETDs

Derivatives of 6-methylbenzo[a]pyrene enriched to 90% carbon-13 at the methyl carbon were synthesized. Reactions of the carcinogen, 6-chloromethylbenzo[a]pyrene, with nucleophiles under solvolytic conditions were studied kinetically and, using labelled 6-chloromethylbenzo[a]pyrene, the reaction products were studied by CMR. The purpose was to characterize the selectivity of the benzo[a]pyrenyl- 6-methyl carbonium ion in its reactions with some simple nucleophiles and with nucleosides and other nucleic acid components.

Although the solvolysis of 6-chloromethylbenzo[a]pyrene in aqueous/organic solution is first order, information about the course of the reaction can be obtained, under certain circumstances, from rate constants. Thus, if the rate of solvolysis is slowed …

Photochemical Studies Of Hydroxo-Bridged Complexes Of Chromium (Iii), Ronald Raymond Ruminski

Chemistry and Chemical Biology ETDs

The acid solution and solid state photolysis in both visible and ultraviolet regions of the spectrum for µ-hydro­xo-bis[pentaamminechromium(III)] chloride, and the solution photolysis in the visible and 1 traviolet region of the spectrum for µ-hydroxo-bis[pentaarnrninechr rnium(III)] perchlorate, have been studied. The ultraviolet irradiation of µ-hydroxo-bis[pentaamminechromium(III)] chloride in HCl and CHlO₄ produces a redox photoproduct identified as HCrO₄^-, although the rate of production of HCrO₄^- in HClO₄ is slower than in HCl. Photochemical cleavage of the hydroxo-bridge occurs in the ultraviolet photolysis of µ -hydroxo-bis[pentaanuninechromium(III)] chloride and is 1.9 times faster than the corresponding …

The Effects Of Various Pyrolysis Conditions On The Release Of Products From Green River Oil Shale, Georgia Thomas Fritz

Chemistry and Chemical Biology ETDs

The fusion of oil shales with eutectic mixtures of inorganic salts was studied with the objective of finding a chemical means of releasing the organic material either at a lower temperature or with a lower empirical activation energy (E_a). Experimental techniques by which the pyrolysis of oil shale was studied were thermogravimetry (TG), evolved gas detection (EGD), and pyrolysis/thin-layer chromatography (TLC). The following fused salts were investigated (ratios in mo1%): LiCO₃/Na₂co₃/K2CO3, 43.5/31.5/25.0; KSCN/NaSCN, 73.75/26.25; KSCN/­NaSCN, 70/30; Na₂SO₄/K₂SO₄/ZnSO₄, 29.1/30.2/40.7; NaCl/Na₂CO_{3 …}

A Study Of The Gas-Solid Reaction Between Hydrogen Sulfide And Mercury(I) Chloride; Development Of A Method For Determination Of Atmospheric Hydrogen Sulfide, Eric H. De Carlo

Chemistry & Biochemistry Theses & Dissertations

The possibility of measuring hydrogen sulfide indirectly by measuring the mercury evolved from the gas-solid reaction between hydrogen sulfide and mercury(I) chloride was studied. DMCS treated glass wool was coated with mercurous chloride and used as a conversion material. The response to hydrogen sulfide was studied as a function of concentration and temperature. The possible interference of other sulfur gases and water was examined.

The studies indicated that hydrogen sulfide could be determined at concentrations as low as 15 ppb. It was found that mercaptans would actively interfere with the hydrogen sulfide to mercury conversion, but that sulfur dioxide would …

Determination Of Size Distributions In Heterodisperse Systems Of Homogeneous, Non-Absorbing Spheres From Angular Light Scattering Extrema, Werner Bergman

Wayne State University Dissertations

No abstract provided.

Comparisons Between Oriented Film And Solution Tertiary Structure Of Various Nucleic Acids, Douglas R. C. Priore

Chemistry and Chemical Biology ETDs

It was desired to help establish whether or not the tertiary structure of a biomolecule is the same in a cry­stal (or an oriented film) as it is in solution. Generally it is accepted that the structures in these diverse environ­ments are similar, if not identical. By comparing the extinction coefficients obtained from oriented film data to those obtained from solution data it was hoped that this question might further be resolved. To this end an electric dichroism instrument built in our lab was used to measure the dichroic signal so as to calculate, with the help of the ultraviolet …

Infrared-To-Visible Upconversion In Rare Earth Doped Materials, Deon G. Ettinger

Chemistry and Chemical Biology ETDs

Upconversion materials have been prepared which may be stimulated by incident 970 nm radiation to emit in the visible region. The couples Yb⁺³-Ho⁺³ in a YF₃ host and Yb⁺³-Er⁺³ in YF₃, YPO₄, Li₃PO₄ and Y₂O₂S hosts have been studied at temperatures from 9K to 273K. For (Y_.80Yb_.19Er_.01)F₃ emission bands at 657 nm, 538 nm, 520 nm, 409 nm and 379 nm have been detected and determined to result from 3-, 2-, 2-, 3-, and 3-photon …

Conversion Of Farnesyl Pyrophosphate And Squalene To Sterols By Rat Liver Microsomal Enzymes: Specificity Of Sterol Carrier Protein₁, Kathleen Lobaugh Gavey

Chemistry and Chemical Biology ETDs

The conversion of farnesyl pyrophosphate to squalene by rat liver microsomes was investigated. The enzyme exhibited an apparent maximum velocity at a substrate concentration of 30 μM. No evidence of substrate inhibition was seen at concentrations up to 65 μM. Phosphatases present in the microsomes or in the 105,000 x g supernatant (S105) did not interfere with squalene synthesis under the experimental conditions used.

s₁₀₅ slightly enhanced the biosynthesis of squalene at the lowest concentrations of microsomal protein studied. The effect was reversed at higher concentrations of microsomes. A 1O-fold increase in the concentration of s₁₀₅ did not …

Charge Transfer Photochemistry Of Some Chromium (Iii) Complexes, Yohn Sik Kang

Chemistry and Chemical Biology ETDs

The photolyses of a series of chromium(III) complexes Cr(en)3 3+, Cr(den)2 3+, Cr(tn)3 3+, and Cr(pn)3 3+, where en= ethylenediamine, den= diethylenetriamine, tn = trimethylenediamine, and pn = propylenediamine, have been investigated. Experiments were carried out on unbuffered and buffered (pH= 2.00) solutions containing 10^-3 – 10^-2 M chromium(III) complexes at room temperature and 10°C. While purging with argon or oxygen, the irradiation was performed with 184.9-253.7 nm u.v. light, corresponding to the charge transfer bands of the complex.

Chromium(Iii) Tartrates, Gerald Lynn Robbins

Chemistry and Chemical Biology ETDs

The binuclear tartrate-bridged complexes [Cr₂ (tartH)₂ (L)₂] and Na[Cr₂ (tart) (tartH) (L)₂]("tart" = C₄H₂O₆^4-, "tartH" = C₄H₃O₆^3- and "L"= 1,10-phenanthroline or 2,2'-bipyridyl) have been synthesized where each complex contains either two optically active or two meso bridging ligands. A discussion of the number of isomers and symmetries of these complexes is presented, as well as a complete description of the syntheses of the complexes and their sodium salts. Steric constraints force the octahedral coordination geometry for the dimer containing two …

Reactions Of N-Ethoxycarbonylthioamides With Dinucleophilic Reagents, Babu George

Chemistry and Chemical Biology ETDs

When an N-ethoxycarbonylthioamide is treated with dinucleophilic reagents containing a primary or secondary amino group and another nucleophilic group, reaction occurs initially between the amino group of the reagent and the thiocarbonyl of the substrate with elimination of hydrogen sulfide and formation of a carbon, nitrogen double bond. The intermediate thus formed may subsequently cyclize in either of two different manners depending upon the relative positions of the two nucleophilic groups in the reagent. A. If the second nucleophilic group is adjacent to the amino group, or separated from it by one carbon atom, cyclization involves nucleophilic attack at the …

Syntheses Directed Toward The Construction Of 1-Deaza-1-Thialysergic Acid, Nicholas Richards Beller

Chemistry and Chemical Biology ETDs

With the goal of synthesizing 1-deaza-1-thialysergic acid (31), a series of substituted 2-stilbazole precursors of 31 was prepared.

313, R₁=SCH₃, R₂=H

314, R₁=SOCH₃, R₂=H

315, R₁=SO₂CH₃, R₂=H

173, R₁=H, R₂=COOC₂H₅

152, R₁ =SCH₃, R₂=COOC₂H₅

162, R₁=SOCH₃, R₂=COOC₂H₅

153, R₁=SO₂CH₃, R₂=COOC₂H₅

In connection with the synthesis …

Studies On Glyoxalase-I, Liang-Po Bebe Han

Chemistry and Chemical Biology ETDs

Glyoxalase-I has been purified 3000-fold from rat erythrocytes by a procedure employing chloroform-ethanol fractionation and chromatography on CM-Sephadex, Sephadex G100, and DEAE-Sephadex. Two major chromatographically distinct glyoxalase-I activity peaks (designated Form I and Form II) were resolved when a shallow linear salt gradient was used on a DEAE-Sephadex A50 column. Form I showed a specific activity of 861 I.U./mg protein and Form II showed a specific activity of 783 I.U./mg protein although neither was purified to homogeneity. Form I and Form II were distinguishable by disc polyacrylamide gel electrophoresis but indistinguishable kinetically. Rat erythrocyte glyoxalase-I was shown to be similar …

A Precipitation Model And Experimental Correlation With Various Properties Of Pentaerythritol Tetranitrate, Thomas Rivera

Chemistry and Chemical Biology ETDs

A continuous precipitation method for the preparation of crystalline pentaerythritol tetranitrate (PETN) has been developed. The process involves the precipitation of PETN from an acetone solution by the addition of water in a static mixer. The principal independent variable is the ratio, R, of the acetone-PETN solution flow rate to the flow rate of water.

A mathematical model based on dispersed plug-flow equations adequately represents the physical process. The relationships developed can be used to predict particle size distributions, two explosion properties of PETN, and estimate the effective kinetics involved in the precipitation process. The mass-weighted mean particle size, L, …

Rearrangements Of Stilbene And Derivatives Following Electron Impact, Gary Alan Braden

Chemistry and Chemical Biology ETDs

The electron impact generated mass spectra of ¹³C- labeled trans-stilbene, bibenzyl, trans-stilbene oxide, 1,2-dibromo-1,2-dyphenylethane, and tolan were studied. Scrambling of the molecular ion prior to fragmentation was examined, and the scrambling pattern occurring was determined wherever possible. Synthesis of 1,α’-¹³C₂-trans-stilbene was accomplished by strating with 1-¹³C- and 2-¹³C-acetic acid. 1,α’-¹³C₂-bibenzyl, starting with 1,α’-¹³C₂-trans-stilbene oxide, 1,α’-¹³C₂-l,2-dibromo-l,2-diphen­ylechane, and 1,α’-¹³C₂-tolan were all synthesized from the dilabeled stilbene. The mass spectral values for the phenyl ion, (pseudo)tropylium ion, (pseudo)phenylethyl …

Reactions Of 2-Aminopyridine With Picryl Halides, Betty Wright Harris

Chemistry and Chemical Biology ETDs

The purpose of this investigation was to study the reaction of 2-aminopyridine with picryl halides with the goal of providing evidence in support of a mechanism accounting for the formation of the observed products. Nuclear magnetic resonance spectroscopy was employed to measure the relative amounts of the various picryl protons in the product mixture, which were assumed to be proportional to the mole percent of the corresponding compounds. 2-Aminopyridine reacted with picryl chloride by a nucleophilic bimolecular substitution reaction to give 2-(N-picrylamino)pyridine as the major product; however, the major product of the reaction of 2-amino­pyridine with picryl fluoride is 1-picryl-2-(N-picrylimino)-1,2-dihydro­pyridine. …

Laser Pyrolysis Gas Chromatography And Plasma Stoichiometric Analysis, Ray Lorain Hanson

Chemistry and Chemical Biology ETDs

Normal-pulse laser interaction with organic solids was studied. Extensive interaction between the carrier gas and the plasma occurred in the quenching process. When hydrogen was used as the carrier gas, significantly greater quantities of products were detected from the laser pyrolysis of graphite and coal compared to laser pyrolysis in helium. Acetylene was shown to be the principal hydrocarbon product from plasma quenching. Equilibrium product distributions calculated at high temperatures by the minimization of free energy revealed that hydrogen and acetylene were the primary gaseous plasma quenching products for hydrocarbons. Organic solids with oxygen present in the molecule yielded carbon …

Composition And Structure Of A Stress Relieving Removable Epoxy Resin, Cecelia Victoria Krapcha Carter

Chemistry and Chemical Biology ETDs

The aqueous modification of polyol modified anhydride cured diglycidyl ether of bisphenol A exhibits properties of a brittle solid when subjected to an impulse stress, and properties of a viscous fluid when subjected to a steady state stress. This behavior is markedly different from the nonaqueous system. Early attempts to understand the nature of the change in properties and the physical mechanism involved have not been completely successful. These attempts have typically taken a physical chemistry approach and have not fully investigated the organic nature of the polymer. In order to fully understand a polymer system an important step should …

Properties Of Intercalated 2h-Nbse2, 4hb-Tas2 And 1t-Tas2, S. F. Meyer, R. E. Howard, G. R. Stewart, Juana Vivó Acrivos, T. H. Geballe

Faculty Publications, Chemistry

The layered compounds 2H-NbSe, 24Hb-TaS, 2and 1T-TaS2 have been intercalated with organic molecules; and the resulting crystal structure, heat capacity, conductivity, and superconductivity have been studied. The coordination in the disulfide layers was found to be unchanged in the product phase. Resistance minima appear and the superconducting transition temperature is reduced in the NbSe2 complex. Conversely, superconductivity is induced in the 4Hb-TaS2 complex. Corresponding evidence of a large change of the density of states, negative for 2H-NbSe2 and positive for 4Hb-TaS2, was also observed upon intercalation. The transport properties of all the intercalation complexes show a pronounced dependence upon the …

Properties Of Hxtas2, D. W. Murphy, F. J. Disalvo, G. W. Hull, J. V. Waszczak, S. F. Meyers, G. R. Stewart, S. Early, Juana Vivó Acrivos, T. H. Geballe

Faculty Publications, Chemistry

The preparation of Hx TaS2 (0 < x < 0.87) is described. The compounds are only marginally stable at room temperature, slowly evolving H2S and H2 (and possibly Hp in air). Magnetic susceptibility data show that a low temperature transformation in 2H ... TaS2 (at so•K) is suppressed with the addition of hydrogen, and· at the same time the superconducting transition temperature T c rises from 0.8 to ~4.2•K at x = 0.11. Heat capacity measurements near this concentration show the superconductivity to be a bulk effect. Finally, by correlation of this data with susceptibility and T c measurements in other intercalation compounds, we suggest that the rise of T c (at low electron transfer) is due to suppression of the low temperature transformation and not due to an excitonic mechanism of superconductivity.

Syntheses And Characterizations Of Vanadyl (Iv) Complexes With Dihydroxydicarboxylate Ligands, Sharon K. Hahs

Chemistry and Chemical Biology ETDs

Binuclear complexes of the vanadyl(IV) tartrates have already been shown to exist both in the solid state and in solution. These complexes consist of two vanadyl(IV) ions bridged by two tartrato(4-) ligands, either of the same--DD (or LL)-- or opposite--DL--enantiomeric configuration. (The meso isomer of tartaric acid will not form binuclear complexes with vanadyl(IV).) The DL complex is more stable than the DD complex due to a greater degree of staggering between the vicinal hydrogen atoms on each tartrate chain. Investigations of vanadyl(IV) complexes with substituted tartaric acid ligands--specifically, (±)-dimethyltartaric acid and (±)-threomethyltartaric acid--have been undertaken to determine whether this …

Electrochemical Investigations Of The Mechanisms Of Reduction Of Benzaldehyde Compounds In Sulfolane, Neal Russell Armstrong

Chemistry and Chemical Biology ETDs

The mechanisms of the reduction of benzaldehyde and several sub­stituted benzaldehydes in the dipolar, aprotic solvent sulfolane, have been investigated. A combination of cyclic voltammetry, transmission spectroelectrochemistry and ring-disk voltammetry was used in this study. Cyclic voltammetric studies indicated that the one-electron benz­aldehyde reduction was followed by a dimerization of the radical anion intermediate to the pinacol. The reduction peak potentials of the benzaldehydes were cathodically shifted in sulfolane compared to values obtained in aqueos media. This indicates an increase in the benzaldehyde reduction energy in the aprotic solvent. The rate of the following chemical reaction was also slower than …

Chronopotentiometric And Chronoamperometric Investigations Of Uranium (Vi) In Molten Condensed Phosphates, John J. Miglio

Chemistry and Chemical Biology ETDs

The diffusion coefficient, D, of U (VI) in molten sodium metaphosphate at 694°C was determined by two independent methods. D was also determined at R values of 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5, where R is the molar M₂O to P₂O₅ ratio and M is univalent. The relative amounts of various phosphate species present in the molten state were determined by thin layer chromatography after rapidly cooling the melt and dissolving the resultant glass in water. With the above information it was hoped to determine if D is inde­pendent of the experimental method of …