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Reduction Pathways in Cyclopentadienyl Rhenium Dicarbonyl Dibromide Deriviatives and Indenyl Rhenium Tricarbonyl: Synthesis, Structure, and Reactivity of Anionic Cyclopentadienyl Rhenium Complexes. Ring Attack vs. Metal-Halogen Exchange

Description: The reactions of diagonal and lateral Cp'Re(CO)2Br2 (where Cp' = n5-C5H5, n5-C5Me5) and (n5-CgH7)Re(CO)3 with reducing agents have been examined. Hydride reduction at -78 °C is observed to occur at the Cp ring in both CpRe(CO)2Br2 isomers, affording a thermally unstable [(n4 -C5Hg)Re(CO)2Br2]- complex. The product of hydride ring attack has been characterized by low-temperature IR and 1H NMR measurements in addition to 13C NOE and heteronuclear 2D NMR measurements. Reaction of lateral CpRe(CO)2… more
Date: December 1989
Creator: Lee, Sang Woo, 1952-
Partner: UNT Libraries
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Analysis of Acid Gas Emissions in the Combustion of the Binder Enhanced d-RDF by Ion Chromatography

Description: Waste-to-energy has become an attractive alternative to landfills. One concern in this development is the release of pollutants in the combustion process. The binder enhanced d-RDF pellets satisfy the requirements of environmental acceptance, chemical/biological stability, and being storeable. The acid gas emissions of combusting d-RDF pellets with sulfur-rich coal were analyzed by ion chromatography and decreased when d-RDF pellets were utilized. The results imply the possibility of using d-RD… more
Date: August 1988
Creator: Jen, Jen-Fon
Partner: UNT Libraries
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Chromatographic and Spectroscopic Studies on Aquatic Fulvic Acid

Description: High Performance Liquid Chromatography (HPLC) was used to investigate the utility of this technique for the analytical and preparative separation of components of aquatic fulvic acids (FA). Three modes of HPLC namely adsorption, anion exchange and reversed phase were evaluated. Aquatic fulvic acids were either extracted from surface water and sediment samples collected from the Southwest of the U.S., or were provided in a high purity form from the USGS. On the adsorption mode, a major fraction… more
Date: August 1986
Creator: Chang, David Juan-Yuan
Partner: UNT Libraries
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Raman Studies of Molecular Dynamics and Interactions in Liquids

Description: In order to explore the N-H stretching region of aliphatic amines, we performed a study of the Raman spectrum of n-propylamine at various concentrations in cyclohexane. Statistical analysis provided evidence of a second symmetric stretching vibration, which we were able to assign to nonhydrogen bonded NH2 groups. To obtain additional evidence on the existence of monomers in n-propylamine and to further study hydrogen bonding and Fermi resonance in aliphatic amines, we extended the investigation… more
Date: May 1984
Creator: Friedman, Barry R. (Barry Richard)
Partner: UNT Libraries
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Thermal and Flash Photolysis Studies of Ligand-Exchange Reactions of Substituted Metal Carbonyl Complexes of Cr and Mo

Description: Thermal and flash photolysis studies of ligand-substitution reactions of cis-(pip)(L)M(CO)_4 by L' (pip = piperidine; L, L' = CO, phosphines, phosphites; M = Cr, Mo) implicate square-pyramidal [(L)M(CO)_4], in which L occupies a coordination site in the equatorial plane, as the reactive species. In chlorobenzene (= CB) solvent, the predominant species formed after flash photolysis and a steady-state intermediate for the thermal reaction is cis—[(CB)(L)M(CO)_4], for which rates of CB-dissociatio… more
Date: May 1989
Creator: Awad, Hani H. (Hani Hanna)
Partner: UNT Libraries
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The Photolytic Ozonation of Organics in Aqueous Solutions

Description: The aim of the investigation described in this work is to gain a better understanding of the processes involved in the oxidation of organic compounds by photolytic ozonation in a laboratory scale reactor. The results and discussions are presented in Chapter III. This chapter contains four parts. In the first part, mass transfer efficiency and the calculation of the mass transfer coefficient, KLa, as well as the ozone decomposition rate constant, KD, are presented and compared with those obtaine… more
Date: May 1980
Creator: Huang, Francis Y.
Partner: UNT Libraries
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Synthesis and Structure of Polynitro- and Polymenthylpolycyclic "Cage" Monomers and Polymers

Description: The objective of this study was to synthesize and characterize new energetic polycyclic "cage" compounds. As part of a program involved in the synthesis of new polynitropolycyclic compounds, 2,6-dinitro-5-methoxy- 7-carbomethoxypentacyclo[5. 3 .0 . 0* • * . CP • i ° . 0* •8]decane has been synthesized. This is a model system which can be used to study (1) the effect of nitro substitution on the photolability of carbon-carbon double bonds and (2) to develop methods for avoiding Haller-Bauer clea… more
Date: May 1987
Creator: Jin, Pei-Wen
Partner: UNT Libraries
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The Preparation, Properties, and Reactions of Silenes, Silenoids, and 2-Silanobornenes

Description: The reaction of chlorodimethylvinylsilane with tertbutyllithium was investigated in the presence of several conjugated dienes. In all cases except with 2,5-dimethylfuran, [2+4] cycloadducts of a silene intermediate are obtained in hydrocarbon solvents. The presence of THF in the reaction mixture suppresses the formation of cycloadducts in favor of 1,3-disilacyclobutanes. In the reaction of dimethylethoxyvinylsilane or dimethylmethoxyvinylsilane with tert-butyllithium the main product is the 1,1… more
Date: December 1981
Creator: Pierce, Richard A. (Richard Austin), 1918-2004
Partner: UNT Libraries
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(4+2)-Cycloaddition Reactions of Ketenes; Pyranones

Description: This study deals with the (4+2)-cycloaddition reactions of 4-π electron compounds with ketenes. Chloroketenes were generated in situ from the corresponding chlorinated acid chlorides in the presence of the ketenophiles. Chloro-, dichloro- and diphenylketenes reacted with 1-methoxy-3-trimethylsiloxy-l,3-butadiene, and 2,4-bis(trimethylsiloxy)-1,3-pentadiene to yield the corresponding dihydropyrans. The dihydropyrans yielded substituted 4-pyranones on hydrolysis.
Date: August 1983
Creator: Agho, Michael O. (Michael Osarenogowu)
Partner: UNT Libraries
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Molecular Dynamics and Interactions in Liquids

Description: Various modern spectroscopies have been utilized with considerable success in recent years to probe the dynamics of vibrational and reorientational relaxation of molecules in condensed phases. We have studied the temperature dependence of the polarized and depolarized Raman spectra of various modes in the following dihalomethanes: dibromomethane, dichloromethane, dichloromethane-d2, and bromochloromethane. Among other observed trends, we have found the following: Vibrational dephasing times cal… more
Date: May 1985
Creator: Chen, Jen Hui
Partner: UNT Libraries
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Regulation of Lactobacillic Acid Formation in Lactobacillus Plantarum

Description: Cyclopropanation of the unsaturated fatty acid moieties of membrane phospholipids is a commonly observed phenomenon in a number of bacterial systems. The cyclopropane fatty acids are usually synthesized during and after the transition from exponential growth to stationary phase, or under such environmental conditions as acidic culture pH, low oxygen tension or high salt concentrations. S-Adenosylmethionine, the ubiquitous methyl group donor, provides the methylene bridge carbon in the reaction … more
Date: December 1980
Creator: Smith, Darwin Dennis
Partner: UNT Libraries
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The Nature of Intermediates Produced Through Ligand-Substitution Reactions of Octahedral Metal Carbonyls

Description: Pulsed laser time-resolved ligand-substitution photochemistry for (DTO)W(CO)4, (DTN)W(CO)4, and (NP)Mo(CO)4 (DTO = 2,2,7,7-tetramethyl-3,6-diathiaoctane; DTN = 2,2,8,8- tetramethyl-3,7-diathianonane; NP = l-diethylamino-2- diphenylphosphinoethane) proceeds via initial fission of the W-S and Mo-P bonds, affording Cs and C4v five-coordinate intermediates for DTN and NP but largely Cs for DTO. The rates of reaction of these intermediates, via chelate ring closure and competitive bimolecular intera… more
Date: May 1986
Creator: Mansour, Saber E. (Saber El-Sayed)
Partner: UNT Libraries
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Reactions of Chloroketenes with Ketene Acetals

Description: The first objective of this investigation was to conduct a systematic study into the reactions of chloroketenes with ketene acetals. The second objective was to explore the synthetic utility of these reaction products and offer a rational explanation for these reaction products.
Date: May 1981
Creator: Watts, Ronald David, 1943-
Partner: UNT Libraries
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The Study of Low Temperature Silene Generation

Description: The reactions of tert-butyl-, sec-butyl-, and n-butyllithium with dimethylfluorovinylsilane include addition to the double bond to give both silene and silenoid intermediates, fluorine substitution, and a novel vinyl substitution. For the tert-butyllithium reaction, product stereochemistry and trapping experiments using both cyclopentadiene and methoxytrimethylsilane show that silenes are not formed in THF. In hexane about 67% of the 1,3-disilacyclobutanes obtained arise from silene dimerizatio… more
Date: August 1985
Creator: Cheng, Albert Home-Been
Partner: UNT Libraries
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Pressure Effects on Electric Field Spectra of Molecular Rydberg States

Description: Electric field studies, electrochromism, were used to obtain excited-state data for analogous divalent sulfur compounds. The sulfides investigated were dimethyl sulfide and small cyclic sulfides including the three to six member ring compounds. The excited-state dipole moments and polarizabilities are reported for the first s, p, and d Rydberg absorption bands which occur in the near vacuum ultraviolet region from 230 to 170 nm. The excited-state data are interpreted in terms of the particular … more
Date: December 1982
Creator: Altenloh, Daniel Dean
Partner: UNT Libraries
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Synthesis and Reactions of Some N-Nitrosamines

Description: Nucleophiles react with the α-acetoxy derivative of α-hydroxybenzylbenzylnitrosamine at the carbonyl carbon of the acetoxy moiety followed by fragmentation to the very same intermediates formed by oxidative metabolism. Since α-acetoxybenzylbenzylnitrosamine has been shown to be able to acylate nucleophiles and since the nucleic acids are nucleophiles, then it is possible that this compound may cause mutations by an acylation pathway instead of or in addition to the more common alkylation pathwa… more
Date: December 1982
Creator: Gunn, Valerie E. (Valerie Elizabeth)
Partner: UNT Libraries
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Studies on Human Plasma Lecithin:Cholesterol Acyltransferase: Physical and Chemical Characterization and Coupled Spectrophotometric Enzyme Assay

Description: The physico-chemical properties of lecithin:cholesterol acyltransferase were investigated. The amino acid composition analysis showed a relatively high content of glutamic acid, aspartic acid, glycine and leucine. The spectrophotometric titration of phenolic groups in the enzyme showed a large increase in absorbance at 295 nm with an apparent pK of about 12.0. The largest change in molar ellipticity at 222 nm was also observed above pH 11. Circular dichroism studies revealed that human lecithin… more
Date: December 1984
Creator: Hara, Shinichi
Partner: UNT Libraries
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GC/MS Analysis of Chlorinated Organic Compounds in Municipal Wastewater After Chlorination

Description: A study has been conducted for the qualitative and Quantitative analysis of chlorinated organic compounds in water. The study included the adaptation of Amberlite XAD macroreticular resin techniques for the concentration of municipal wastewater samples, followed by GC/MS analysis. A new analytical method was developed for the determination of volatile halogenated organics using liquid-liquid extraction and electron capture gas chromatography. And, a computer program was written which searches r… more
Date: August 1982
Creator: Henderson, James E. (James Edward)
Partner: UNT Libraries
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Synthesis of Anthracyclines Related to Adriamycin

Description: This dissertation reports the preparation of several types of anthraquinones structurally related to adriamycin. It describes the synthesis of two types of 2-aminoquinizarin compounds. It also presents two new syntheses of a heterocyclic tetracyclic ring system, similar to the aglicone ring system of adriamycin. A series of 2-aminoquinizarins was prepared by adding several primary amines to quinizarin. Quinizarin was shown to be essentially inert toward secondary amines. Several secondary amine… more
Date: May 1981
Creator: White, Roger J.
Partner: UNT Libraries
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Silenes and Silenoids in the Chemistry of Cyclopentadienylsilanes

Description: Evidence is presented that apparent silene products obtained from the metalation of cyclopentadienyldimethyl - chlorosilane either with tert-butyl1ithium or with methylenetriphenylphosphorane actually arise from the metalated starting material, a silenoid, rather than from a silafulvene intermediate. Trimethylmethoxysi1ane is shown to be an effective trap for dimethylsilafulvene. A new dimethylsilafulvene precursor, bis(dimethylmethoxysi1yl) cyclopentadiene, which gives high yields of dimethyld… more
Date: August 1986
Creator: Rozell, James M. (James Morris)
Partner: UNT Libraries
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Spectroscopic and Physical Effects of Highly Polar Groups

Description: Since the development of the understanding that the electron distribution within a molecule is chiefly responsible for its properties and behavior, factors influencing this charge distribution have been of interest to scientists. The chemical reactivity of a molecule, the physical properties, and to a large extent, structure and geometry, are all functions of the electron distribution. This study examines the issue of electronic structure from two points of view, each of them focussing on a spe… more
Date: December 1981
Creator: Schander, Judith Turner
Partner: UNT Libraries
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Synthesis of Ketene Thioacetals and Their Monosulfoxide Derivatives and the Thermal Rearrangements of Diallylic Ketene Thioacetals

Description: Ketene dimethyl thioacetal monosulfoxide was prepared in 68% overall yield in two steps starting from methylmagnesium chloride. The yield of dithioacetic acid was improved significantly by employing tetrahydrofuran as solvent and using elevated temperatures. A one-pot synthesis of ketene thioacetals from alkyl halides was developed and several ketene thioacetals were prepared by this method. Direct oxidation of ketene thioacetals using m-chloroperoxybenzoic acid provided a general route to kete… more
Date: August 1982
Creator: Kaya, Riza
Partner: UNT Libraries
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Intramolecular 2+2 Cycloadditions of Ketenes

Description: The objective of this study was to explore intramolecular ketene cycloadditions with the anticipated results of developing new synthetic methodology for the synthesis of polycyclic compounds difficult to obtain by other procedures. (o-Alkenylphenoxy)ketenes were initially selected for this study because these ketenes provided a favorable proximity for the intramolecular [2+2] cycloaddition reactions. The difunctional precursors, (o-alkenylphenoxy)- acetic acids, were readily prepared from o-alk… more
Date: December 1986
Creator: Giang, Yun-Seng F. (Yun-Seng Frank)
Partner: UNT Libraries
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Pyrolysis Capillary Chromatography of Refuse-Derived Fuel and Aquatic Fulvic Acids

Description: Pyrolysis-capillary gas chromatography combined with FID, ECD and MS detection were used to characterize refuse-derived fuel and aquatic fulvic acids. Different pyrolysis methods and programs were evaluated. Pyrolysis temperatures of 700-800°C produced the strongest signal for organics present in RDF and fulvic acid. Cellulose and fatty acids pyrolyzates were identifiable by GC-MS following preparative pyrolysis fractionation. At organic chloride content of 0.023%, only three halogenated compou… more
Date: December 1989
Creator: Haj-Mahmoud, Qasem M. (Qasem Mohammed)
Partner: UNT Libraries
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