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 Degree Discipline: Chemistry
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Infrared Studies of Anions of Organic Acids

Infrared Studies of Anions of Organic Acids

Date: August 1962
Creator: Dyke, Maurice Arthur
Description: The present work is a part of a systematic investigation of the frequency shifts in infrared absorption produced by changing to the anions carbonyl containing acidic compounds.
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Infrared Studies of Group VIB metal Carbonyl Derivatives

Infrared Studies of Group VIB metal Carbonyl Derivatives

Date: August 1971
Creator: Brown, Richard Arthur
Description: With three different proposals for the bonding in metal carbonyls, it was decided to look into the situation more thoroughly in order to see what other evidence was available to support or refute any of these ideas. It became obvious that a definite contradiction existed between the kinetic evidence of various metal carbonyls, and the concept of MC bond strengths as predicted by Cotton's theory.
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An Infrared Study of some Ω-Phenyl and Ω-Benzoyl Alkanoic Acids

An Infrared Study of some Ω-Phenyl and Ω-Benzoyl Alkanoic Acids

Date: August 1963
Creator: Chanslor, Robert Janes
Description: There is no available information in the literature on interaction between carboxyl hydrogen and ω-phenyl groups. Consequently, it was of interest to seek such interactions. Some form of interaction is evident from the study of the spectra of some phenylalkanoic acids and benzoyalkanoic acids.
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Inhibitors of Dihydrofolate Reductase, 8-Oxapteridines

Inhibitors of Dihydrofolate Reductase, 8-Oxapteridines

Date: December 1974
Creator: Lin, Shwu-Ching H.
Description: The biological activities of some homeosterically related analogs of dihydrofolic acid have been examined involving pyrimido[4,5-b][l,4]oxazine (8-oxapteridine) derivatives. It is anticipated that these compounds might interfere with the essential intermediary metabolic functions of the vitamin and thus serve as potential chemotherapeutic agents. Preliminary toxicity studies in microbial assay systems were disappointing; however, inhibitory effects were demonstrated in cell free enzyme systems. A comparison of the structure/activity relationships was determined using two folic acid coenzyme systems, dihydrofolate reductase and thymidylate synthetase. The 2-amino-4-hydroxy-6-(substituted)-8-oxapteridines were generally more effective inhibitors than the corresponding 2,4-diamino analogs. The relative biological activity of a series of 2-amino-4-hydroxy-6-ω-phenylalkyl derivatives were examined, and the most active derivative was the 6-phenylethyl analog which appears to function as a mixed-type inhibitor involving partially competitive and partially non-competitive inhibition.
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Interaction of learning approach with concept integration and achievement in a large guided inquiry organic class.

Interaction of learning approach with concept integration and achievement in a large guided inquiry organic class.

Date: August 2009
Creator: Mewhinney, Christina
Description: A study was conducted to investigate the relationship of students' concept integration and achievement with time spent within a topic and across related topics in a large first semester guided inquiry organic chemistry class. Achievement was based on evidence of algorithmic problem solving; and concept integration was based on demonstrated performance explaining, applying, and relating concepts to each other. Twelve individual assessments were made of both variables over three related topics - acid/base, nucleophilic substitution and electrophilic addition reactions. Measurements included written, free response and ordered multiple answer questions using a classroom response system. Results demonstrated that students can solve problems without conceptual understanding. A second study was conducted to compare the students' learning approach at the beginning and end of the course. Students were scored on their preferences for a deep, strategic, or surface approach to learning based on their responses to a pre and post survey. Results suggest that students significantly decreased their preference for a surface approach during the semester. Analysis of the data collected was performed to determine the relationship between students' learning approach and their concept integration and achievement in this class. Results show a correlation between a deep approach and concept integration and a ...
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Interactions of Clean and Sulfur-modified Reactive Metal Surfaces with Aqueous Vapor and Liquid Environments : A Combined Ultra-high Vacuum/electrochemistry Study

Interactions of Clean and Sulfur-modified Reactive Metal Surfaces with Aqueous Vapor and Liquid Environments : A Combined Ultra-high Vacuum/electrochemistry Study

Date: May 1998
Creator: Lin, Tien-Chih, 1966-
Description: The focus of this research is to explore the molecular-level interactions between reactive metal surfaces and aqueous environments by combined ultra-high vacuum/electrochemistry (UHV-EC) methodology. The objectives of this work are to understand (1) the effects of sulfate ions on the passivity of metal oxide/hydroxide surface layer, (2) the effects of sulfur-modification on the evolution of metal oxide/hydroxide surface layer, and (3) the effects of sulfur adsorbate on cation adsorption at metal surfaces.
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Interfacial Studies of Bimetallic Corrosion in Copper/Ruthenium Systems and Silicon Surface Modification with Organic and Organometallic Chemistry

Interfacial Studies of Bimetallic Corrosion in Copper/Ruthenium Systems and Silicon Surface Modification with Organic and Organometallic Chemistry

Access: Use of this item is restricted to the UNT Community.
Date: August 2006
Creator: Nalla, Praveen Reddy
Description: To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for ...
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Intermediates for Paracyclophane Synthesis

Intermediates for Paracyclophane Synthesis

Date: August 1962
Creator: Lin, Ying-tsung
Description: It is proposed in this thesis that the imperfect systems of Cram and of Schubert be combined with some modifications.
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Intramolecular 2+2 Cycloadditions of Ketenes

Intramolecular 2+2 Cycloadditions of Ketenes

Date: December 1986
Creator: Giang, Yun-Seng F. (Yun-Seng Frank)
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-alkenylphenols and ∝-halocarboxylic acids and were converted to the corresponding acid chlorides by reaction with oxalyl chloride. The acid chlorides were dehydrochlorinated to the corresponding (o-alkenylphenoxy)ketenes by treatment with triethylamine. The ketenes undergo a facile intramolecular [2+2] cycloaddition to give polycyclic eye 1obutanones. The (o-vinylphenoxy)ketenes are clearly more reactive than the (o-allylphenoxy)ketenes and provide much better yields of the cycloaddition products because of electronic effects in the transition state in the cycloaddition process. The intramolecular [2+2] cycloadditions of keteniminium salts were included in this study as a more electrophilic alternative to ketenes that will react with less nucleophilic carbon-carbon double bonds. However, the use of keteniminium salts instead of ketenes in Intramolecular cycloadditions does have some limitations. The synthesis of benzofurans via the intramolecular [2+2] cycloadditions of (o-acylphenoxy)ketenes was accomplished. The initially formed ß-lactone cycloaddition products spontaneously underwent ...
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Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes

Intramolecular [2+2] Cycloadditions of Phenoxyketenes and Intermolecular [2+2] Cycloadditions of Aminoketenes

Date: May 1989
Creator: Gu, Yi Qi
Description: One objective of this study was to explore the intramolecular [2+2] cycloadditions of phenoxyketenes to carbonyl groups with isoflavones and benzofurans as target compounds. The other objective was to investigate the eyeloaddition reactions of rarely studied aminoketenes. The conversion of 2-(carboxyalkoxy)benzils to the corresponding phenoxyketenes leads to an intramolecular [2+2] cycloaddition to ultimately yield isoflavones and/or 3-aroylbenzofurans. The product distributions are dependent upon the substitution pattern in the original benzil acids. The initial cycloaddition products, β-lactones, are isolated in some instances while some β-lactones spontaneously underwent decarboxylation and could not be isolated. The ketene intermediate was demonstrated in the intramolecular reaction of benzil acids or ketoacids with sodium acetate and acetic anhydride. It is suggested that sodium acetate and acetic anhydride could serve as a source for the generation of ketenes directly from certain organic acids. The treatment of ketoacids with acetic anhydride and sodium acetate provides a simpler procedure to prepare benzofurans than going through the acid chloride with subsequent triethylamine dehydrochlorination to give the ketenes. N-Ary1-N-alkylaminoketenes were prepared for the first time from the corresponding glycine derivatives by using p-toluenesulfonyl chloride and triethylamine. These aminoketenes underwent in situ cycloadditions with cyclopentadiene, cycloheptene and cyclooctenes to yield only the ...
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Investigating Molecular Structures: Rapidly Examining Molecular Fingerprints Through Fast Passage Broadband Fourier Transform Microwave Spectroscopy

Investigating Molecular Structures: Rapidly Examining Molecular Fingerprints Through Fast Passage Broadband Fourier Transform Microwave Spectroscopy

Date: May 2011
Creator: Grubbs, Garry Smith, II
Description: Microwave spectroscopy is a gas phase technique typically geared toward measuring the rotational transitions of Molecules. The information contained in this type of spectroscopy pertains to a molecules structure, both geometric and electronic, which give insight into a molecule's chemistry. Typically this type of spectroscopy is high resolution, but narrowband ≤1 MHz in frequency. This is achieved by tuning a cavity, exciting a molecule with electromagnetic radiation in the microwave region, turning the electromagnetic radiation o, and measuring a signal from the molecular relaxation in the form of a free induction decay (FID). The FID is then Fourier transformed to give a frequency of the transition. "Fast passage" is defined as a sweeping of frequencies through a transition at a time much shorter (≤10 s) than the molecular relaxation (≈100 s). Recent advancements in technology have allowed for the creation of these fast frequency sweeps, known as "chirps", which allow for broadband capabilities. This work presents the design, construction, and implementation of one such novel, high-resolution microwave spectrometer with broadband capabilities. The manuscript also provides the theory, technique, and motivations behind building of such an instrument. In this manuscript it is demonstrated that, although a gas phase technique, solids, liquids, ...
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Investigation of Copper Out-Plating Mechanism on Silicon Wafer Surface

Investigation of Copper Out-Plating Mechanism on Silicon Wafer Surface

Date: August 1995
Creator: Chien, Hsu-Yueh
Description: As the miniaturization keeps decreasing in semiconductor device fabrication, metal contamination on silicon surfaces becomes critical. An investigation of the fundamental mechanism of metal contamination process on silicon surface is therefore important. Kinetics and thermodynamics of the copper out-plating process on silicon surfaces in diluted HF solutions are both evaluated by several analytical methods.
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Investigation of Structure and Properties of Low Temperature Deposited Diamond-Like Carbon Films

Investigation of Structure and Properties of Low Temperature Deposited Diamond-Like Carbon Films

Date: August 2004
Creator: Pingsuthiwong, Charoendee
Description: Electrodeposition is a novel method for fabrication of diamond-like carbon (DLC) films on metal substrates. In this work, DLC was electrochemically deposited on different substrates based on an anodic oxidation cyclization of acetylene in liquid ammonia. Successfully anodic deposition was carried out for DLC onto nickel substrate at temperatures below -40°C. Comparative studies were performed on a series of different carbon sources (acetylene, sodium acetylide, and a mixture of acetylene and sodium acetylide). The films were characterized using a variety of methods including Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), XPS valence band spectra, and/or scanning electron microscopy (SEM). Raman spectroscopy is used as a bench mark technique to verify the presence of deposited DLC films, to access the films homogeneities, and to provide the ratio of the different carbon phases, mainly disordered graphite (D) and graphite (G) phases in the films. A combination of the Raman with FTIR and valence band spectra analysis allowed the distinction between hydrogenated DLC and unhydrogenated DLC films. Three different kinds of DLC [(1) hydrogenated DLC (a-C:H); (2) tetrahedral hydrogenated DLC (ta-C:H); and (3) graphitic-like DLC] were deposited depending upon the deposition conditions and substrates. Temperature and current density are ...
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Investigation of the Possible Application of High and Low Frequency Conductance Measurements to the Analysis of Poly-Component Systems

Investigation of the Possible Application of High and Low Frequency Conductance Measurements to the Analysis of Poly-Component Systems

Date: 1956
Creator: Pinkerton, K. Allan
Description: The immediate goal of this thesis was the analysis of a three-component system whose major component was water. This analysis was to be the result of a procedure which could be readily extended to more complex systems.
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Investigation of the Pressure Dependence of SO3    Formation

Investigation of the Pressure Dependence of SO3 Formation

Date: December 2003
Creator: Naidoo, Jacinth
Description: The kinetics of the pressure dependent O + SO2 + Ar reaction have been investigated using laser photolysis resonance fluorescence at temperatures of 289 K, 399 K, 581 K, 699 K, 842 K and 1040 K and at pressures from 30-665 torr. Falloff was observed for the first time in the pressure dependence. Application of Lindemann theory yielded an Arrhenius expression of k(T) = 3.3 x 10-32exp(-992/T) cm6 molecule-1 s-1 for the low pressure limit and k(T) = 8.47 x 10-14exp(-468/T) cm3 molecule-1 s-1 for the high pressure limit at temperatures between 289 and 842 K. The reaction is unusual as it possesses a positive activation energy at low temperature, yet at higher temperatures the activation energy is negative, illustrating a reaction barrier.
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Investigation of Ultratrace Metallic and Organic Contaminants in Semiconductor Processing Environments

Investigation of Ultratrace Metallic and Organic Contaminants in Semiconductor Processing Environments

Date: May 1997
Creator: Xu, Fei, 1971-
Description: Detection of ultratrace levels of metallic ion impurities in hydrofluoric acid solutions and alkaline hydrogen peroxide solution was demonstrated using a silicon-based sensing electrode. The sensor's operation principle is based on direct measurements of the silicon open-circuit potential shift generated by the interaction between metallic ions and the silicon-based sensing surface. The new sensor can have practical applications in the on-line monitoring of microelectronic chemical processing. The detection of Ag+ content in KODAK waste water was carried out successfully by this novel sensor. Trace levels of organic impurities in the hydrofluoric acid solutions and in the cleanroom air were characterized by multiple internal reflection infrared spectroscopy (MIRIS) using an organics probe prepared directly from a regular silicon wafer.
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Investigations of Thermochemistry and the Kinetics of H Atom Radical Reactions

Investigations of Thermochemistry and the Kinetics of H Atom Radical Reactions

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Date: December 2002
Creator: Peebles, Lynda Renee
Description: The thermochemistry of several species, and the kinetics of various H atom radical reactions relevant to atmospheric and combustion chemistry were investigated using ab initio theoretical techniques and the flash photolysis / resonance fluorescence technique. Using ab initio quantum mechanical calculations up to the G3 level of theory, the C-H bond strengths of several alkanes were calculated. The bond strengths were calculated using two working reactions. From the results, it is apparent that the bond strengths decrease as methyl groups are added to the central carbon. The results are in good agreement with recent experimental halogenation kinetic studies. Hydrogen bond strengths with sulfur and oxygen were studied via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results for the bond dissociation energies (ground state at 0 K, units: kJ mol-1) are: S-H = 349.9, S-D = 354.7, HS-H = 376.2, DS-D = 383.4, and HO-H = 492.6. These data compare well with experimental literature. The rate constants for the isotopic reactions of H + H2S, D + H2S, H + D2S, and D + D2S are studied at the QCISD(T)/6-311+G(3df,2p) level of theory. The contributions of the exchange reaction versus abstraction are examined through transition state ...
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Isolation and Characterization of Proteus vulgaris Methylglyoxal Synthetase

Isolation and Characterization of Proteus vulgaris Methylglyoxal Synthetase

Date: May 1975
Creator: Tsai, Pei-Kuo
Description: Methylglyoxal synthetase, which catalyzes the formation of methylglyoxal and inorganic phosphate from dihydroxyacetone phosphate, was found in extracts of Proteus vulgaris. An efficient purification procedure utilizing ion exchange column chromatography and isoelectric focusing has been developed. Homogeneity of the enzyme preparation was confirmed by polyacrylamide gel electrophoresis and rechromatography.Two components of methylglyoxal synthetase were obtained upon isoelectric focusing. A comparison of the chemical and physical properties of the two components was carried out. The enzyme is a dimer. In the presence of inorganic phosphate, the hyperbolic saturation kinetics with dihydroxyacetone phosphate are shifted to sigmoidal.
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The Isolation and Chemical Study of Compounds Produced by a Strain of Penicillium Notatum

The Isolation and Chemical Study of Compounds Produced by a Strain of Penicillium Notatum

Date: 1946
Creator: Jones, James Hollis
Description: It is the purpose of this paper to present data on the isolation and study of the chemical nature of compounds produced by this strain of mold which resembles Penicillium notatum nestling.
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Isozymes and In Vivo Activity of Triosephosphate Isomerase

Isozymes and In Vivo Activity of Triosephosphate Isomerase

Date: May 1974
Creator: Snapka, Robert Morris
Description: The distribution of isozymes of triosephosphate isomerase was normal in all human tissues examined. This finding argues against the existence of tissue-specific isozymes. Normal distributions of isozymes were also found in patients with cri-du-chat syndrome. Thus it is unlikely that a gene for triosephosphate isomerase is located on the short arm of chromosome five in man. When triosephosphate isomerases from a wide range of species were examined by starch gel electrophoresis, definite evolutionary patterns were found. Kinetic studies were conducted on human triosephosphate isomerase under conditions simulating the intracellular environment of the erythrocyte. Calculations using the kinetic parameters obtained indicate that even in triosephosphate isomerase deficiency disease, enough enzyme activity remains that the rate of glycolysis should not become inhibited.
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Ketene Carbodiimide Cycloadditions

Ketene Carbodiimide Cycloadditions

Date: August 1970
Creator: Dorsey, Edwin Darrell
Description: It was proposed to study the cycloaddition of ketenes and carbodiimides in some detail. The first objective was to investigate the general applicability of the reaction as a tool for the synthetic organic chemist in the preparation of a new class of substituted β-lactams; i.e., imino-β-lactams. It was proposed for this part of the research problem to look for the intermediate, either directly or indirectly, by trapping experiments. It was further proposed to study substituent effects in the ketene and carbodiimide and also Investigate the effect of solvent polarity on the reaction rate. From these data, it was hoped that the mechanism of the cycloaddition reaction could be elucidated.
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Ketene Reactions: I. The Addition of Acid Chlorides to Dimethylketene ; II. The Cycloaddition of Ketenes to Carbonyl Compounds

Ketene Reactions: I. The Addition of Acid Chlorides to Dimethylketene ; II. The Cycloaddition of Ketenes to Carbonyl Compounds

Date: December 1970
Creator: Smith, Larry
Description: Part I describes the addition of several acid chlorides to dimethylketene. The resulting 3-ketoacid chlorides were isolated and characterized. Part II describes the cycloaddition of several aldoketenes to chloral. The ketenes were generated in situ by dehydrohalogenation and dehalogenation of appropriately substituted acyl halides.
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Kinetic Investigation of the Gas Phase Atomic Sulfur and Nitrogen Dioxide Reaction

Kinetic Investigation of the Gas Phase Atomic Sulfur and Nitrogen Dioxide Reaction

Date: May 2011
Creator: Thompson, Kristopher Michael
Description: The kinetics of the reaction of atomic sulfur and nitrogen dioxide have been investigated over the temperature range 298 to 650 K and pressures from 14 - 405 mbar using the laser flash photolysis - resonance fluorescence technique. The overall bimolecular rate expression k (T) = (1.88 ± 0.49) x10-11 exp-(4.14 ± 0.10 kJ mol-1)/RT cm3 molecule-1 s-1 is derived. Ab initio calculations were performed at the CCSD(T)/CBS level of theory and a potential energy surface has been derived. RRKM theory calculations were performed on the system. It is found that an initially formed SNO2 is vibrationally excited and the rate of collisional stabilization is slower than the rate of dissociation to SO + NO products by a factor of 100 - 1000, under the experimental conditions.
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Kinetic studies and computational modeling of atomic chlorine reactions in the gas phase.

Kinetic studies and computational modeling of atomic chlorine reactions in the gas phase.

Date: August 2009
Creator: Alecu, Ionut M.
Description: The gas phase reactions of atomic chlorine with hydrogen sulfide, ammonia, benzene, and ethylene are investigated using the laser flash photolysis / resonance fluorescence experimental technique. In addition, the kinetics of the reverse processes for the latter two elementary reactions are also studied experimentally. The absolute rate constants for these processes are measured over a wide range of conditions, and the results offer new accurate information about the reactivity and thermochemistry of these systems. The temperature dependences of these reactions are interpreted via the Arrhenius equation, which yields significantly negative activation energies for the reaction of the chlorine atom and hydrogen sulfide as well as for that between the phenyl radical and hydrogen chloride. Positive activation energies which are smaller than the overall endothermicity are measured for the reactions between atomic chlorine with ammonia and ethylene, which suggests that the reverse processes for these reactions also possess negative activation energies. The enthalpies of formation of the phenyl and β-chlorovinyl are assessed via the third-law method. The stability and reactivity of each reaction system is further rationalized based on potential energy surfaces, computed with high-level ab initio quantum mechanical methods and refined through the inclusion of effects which arise from the ...
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