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Spectrofluorometric and Solubility Studies of Polycyclic Aromatic Hydrocarbons in Hydrogen Bonded Binary Solvent Mixtures

Description: The purpose of this dissertation is to investigate the behavior of polycyclic aromatic hydrocarbons (PAHs) in binary solvent systems and determine and/or develop predictive mathematical expressions for describing solutions in which hydrogen-bonding occurs.
Date: May 1997
Creator: Powell, Joyce R., 1968-

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 specific component within the molecules studied. In the present work, the effects of the highly polar carbonyl group on spectroscopic parameters and physical behavior are investigated. An additional area of study is the effect of fluorine substitution on the energy levels of some halogenated ethylenes. The specific parameters examined are the ionization potentials, the absorption frequencies, and the energies of a class of excited states known as molecular Rydberg states. It was during the study of these halogenated ethylenes that the observations leading to the carbonyl compound investigations were made, so that the two areas examined are connected both experimentally and chemically.
Date: December 1981
Creator: Schander, Judith Turner

The Stereochemistry of Silenes and Alpha-Lithio Silanes

Description: When E- or Z-l-methyl-l-phenyl-2-neopentylsilene was generated by the retro-Diels-Alder vacuum-sealed tube thermolysis of its corresponding anthracene adduct, in the presence of various alkoxysilanes, only one diastereomeric adduct was formed in each case, showing that the reactions are stereospecific. An x-ray crystal structure of the methoxytriphenylsilane adduct of the E-silene confirmed its relative configuration as (R,S) or (S,R). This demonstrated that the addition of alkoxysilanes to silenes is stereospecific and syn. The relative configurations of similar alkoxysilane and alkoxystannane adducts to E- and Z-l-methyl-l-phenyl-2-neopentylsilene were assigned based on a combination of xray structures and *3C NMR data. A strong, nonbonded oxygen-metal interaction is apparent in all of those compounds studied. Treatment of the alkoxystannane adducts with alkyl lithium reagents results in tin-lithium exchange in some cases. The results indicate that the resulting <x-lithio alkoxysilanes are not configurationally stable in either THF or hydrocarbon solvents. The reaction of tert butyl lithium with a-trimethylsilylvinylmethylphenylchlorosilane in hydrocarbon solvents yields E- and Z-l-methyl-l-phenyl-2-neopentyl-2-trimethylsilylsilene. In the absence of any traps these silenes undergo a novel tert butyl lithium catalyzed rearrangement to 2-phenyl-3-trimethylsilyl-5,5-dimethyl-2-silahex-3-ene. These silenes were also trapped as their [4+2] cycloadducts with anthracene. The Z-isomer of the anthracene adduct was separated and its stereochemistry confirmed by an x-ray crystal structure. The anthracene adducts of both E- and Z-l-methyl-1-phenyl-2-neopentyl-2-trimethylsilylsilene undergo a facile, stereospecific decomposition at temperatures as low as 190°C to regenerate their respective silenes, the mildest stereospecific route to a silene yet reported. The E- and Z-silenes react stereospecifically with methanol under vacuum-sealed tube conditions. The stereochemistry of the addition is syn and a common mechanism is proposed for the addition of alcohols and the addition of alkoxysilanes to silenes.
Date: May 1987
Creator: Bates, Tim Frank

Stereoselective Solid-State NaBH₄ Reduction of 1-Methylpentacyclo[5.4.0.0²,⁶.0³,¹⁰,0⁵,⁹]undecane-8, 11-Dione, Synthesis and Chemistry of Strained Alkenes, and Chemical and Microbial Synthesis of Racemic and Optically Active (S)-4-Hydroxy-2-Cyclohexenone

Description: Part I. Reduction of the 1-methylpentacyclo [5.4.0.0²,⁶.0³,¹⁰,0⁵,⁹]undecane-8, 11-dione (9) with solid NaBH₄ resulted in highly stereoselective reduction of both C=O groups in the substrate, thereby affording the corresponding endo-8, endo-11-diol (11a). The configuration of 11a was established unequivocally by converting 11a into the corresponding cyclic thiocarbonate ester, 12. Part II. Z-1,2-Di(1'-adamantyl)ethene (14) was synthesized with a high degree of stereoselectively in four steps (Scheme 9 in Chapter 2). E-1,2-di(1'-adamantyl)ethene (15) was synthesized by iodine promoted isomerization of 14. Both structures were established unequivocally via single-crystal X-ray structural analysis. E-1-(exo-8'-Pentacyclo[5.4.0.0²,⁶.0³,¹⁰,0⁵,⁹]undecyl)-2-phenylethylene (16a) was synthesized, and its structure was established via analysis of its 1H, 13C, and 2D COSY NMR spectra. Part III. Reactions of electrophiles, i.e.,:CCl_2, PhSCl, and Br_2, to Z- and E-1,2-di(1'-adamantyl)ethenes (14 and 15, respectively) are described (Scheme 5, 8, 10, and 13 in Chapter 3). Structures of the corresponding products were established unequivocally via analysis of their respective one- and two-dimensional NMR spectra and/or single-crystal X-ray structural analysis. Part IV. An improved asymmetric synthesis of optically active (S)-4-hydroxy-2-cyclohexenone 1 (64%ee, determined via Mosher's method) has been developed (Scheme 5 in Chapter 4). The key step in this synthesis involves the baker's yeast reduction of 13. The absolute configuration of the major product, (S)-1, was established unequivocally via single-crystal X-ray structural analysis of a precursor. The optical purity of the major product 14a (80%de, 67%ee) was established via careful integration of relevant gated-decoupled 13C NMR spectra.
Date: August 1995
Creator: Xing, Dongxia

Structural Elucidation of tert-Butyllithium/Lithium Alkoxide and Lithium Hydride/Lithium Alkoxide Mixed Aggregates

Description: The effects of lithium alkoxides on the rates of reactions and on the structures of a series of tert-butyllithium/lithium alkoxide mixed aggregates were studied, where the alkoxides were iso-butoxide, tert-butoxide and menthoxide. It was found that their effects depend not only on their amount present, but also on their steric bulk. The tert-butyllithium/lithium alkoxide mixed aggregates were exposed to UV light or heat to form lithium hydride/lithium alkoxide mixed aggregates. The aggregation states were assigned from either 13C-6Li coupling or a new technique based on the relative intensity of NMR peaks using different nuclei. The compounds formed depend upon the method of formation and the alkoxide. The unique properties of the lithium hydride/lithium alkoxide mixed aggregates are their high solubility in hydrocarbon solutions, very reactive bases, showing 6Li-1H couplings, and having only one hydride ion per aggregate. Their formation, reactivity, solubility, and aggregation states were found to depend on the size of lithium alkoxides. X-ray crystal structures of lithium tert-butoxide and lithium menthoxide were also studied and found to be hexameric.
Date: December 1997
Creator: Nguyen, Hanh D.

Studies of Nitrogen-containing Compounds Having Pyrethroid-like Bioactivity

Description: During recent years most of the successful developments in pyrethroids have been primarily concerned with structural or compositional variations. As a part of our continuing interest in pyrethroid insecticides, nitrogen-containing compounds having pyrethroid-like structures were synthesized. Seven prolinate compounds, N-(substituted)-phenyl-prolinates and N-carbobenzoxy-prolinates were coupled with known pyrethroid alcohols. These structural variations which "locked in" a specific conformation between the nitrogen and chiral a-carbon in the acid moiety of fluvalinate were studied to determine the influence of certain conformations on insecticidal toxicity. The toxicity data for the prolinate compounds showed intermediate mortality against nonresistant cockroaches. It was concluded that the conformation imposed by the proline ring portion of the esters was probably close to the favored conformation for interaction of fluvalinate-like pyrethroids with the insect receptor site. A second series of nitrogen-containing compounds, twenty-five carbamate esters resulting from the condensation of N-isopropyl-(substituted)-anilines and N-alkyl-(substituted)-benzylamines with appropriate pyrethroid alcohols were studied for insecticidal activity. These studies were conducted on pyrethroid-susceptible houseflies. Some of the carbamate esters exhibited high toxicity when synergized by piperonyl butoxide. For example, the toxicity ( LD 50 ) of O-a-cyano-3-phenoxyfaenzyl-N-a,a-dimethyl-4-bromo-benzyl carbamate was 0.012 ug/g, which is significantly greater than that reported for the potent pyrethroid, fenvalerate. Correlations of insecticidal activity with respect to structure and conformational factors of the carbamate esters have been made. The N-isopropyl substituent decreases insecticidal activity in the N-benzyl-derived compounds, while the N-isopropyl substituent enhances activity in the N-phenyl-derived compounds. Certain substituents on the phenyl ring of both analogs greatly affect insecticidal potency of the carbamate esters. Also, some alkyl substituents (especially, a,cx-dimethyl and a-cyclopropyl groups) on the benzylic carbon of the benzylamine series enhance toxicity. The a,a-dimethyl branching of the N-benzyl carbamate approximates the steric shape given by the gemdimethyl group for conventional cyclopropane ring-containing pyrethroids. The N-benzyl compounds are significantly synergized by ...
Date: August 1989
Creator: Lee, Jimmy Jing-Ming, 1955-

Studies of Solvent Displacement from Solvated Metal Carbonyl Complexes of Chromium, Molybdenum, and Tungsten

Description: Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.
Date: August 1990
Creator: Zhang, Shulin

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:cholesterol acyltransferase has a relatively high content of β-pleated sheet structure (48%) with 20% α-helix, and 32% remaining structure. Human lecithin:cholesterol acyltransferase has a high extinction coefficient at neutral pH. Microsequencing of the amino terminal residues of the enzyme revealed a hydrophobic character. Inactivation of lecithin:cholesterol acyltransferase activity was observed using diisopropylfluorophosphate with a stoichiometry of 1 mole of diisopropylphosphate incorporated per mole of enzyme. This suggests the involvement of a serine residue in the active site of the enzyme, possibly for the formation of an acyl-intermediate. A new quicker assay method for lecithin:cholesterol acyltransferase was developed. This assay involved coupling reaction with acyl CoA synthetase, ΡΡᵢ-dependent phosphofructokinase, aldolase, triosephosphate isomerase and α-glycerol-3-phosphate dehydrogenase monitoring a change in the absorbance or fluorescence intensity due to the oxidation of NADH. The activity of each coupling enzyme was accurately determined to establish the optimum assay condition for lecithin:cholesterol acyltransferase. The coupled enzyme assay for lecithin:cholesterol acyltransferase by spectrofluorometry showed a significant change in relative fluorescence intensity whereas a UV absorption spectroscopy method showed no significant absorbance change for the initial rate of lecithin:cholesterol acyltransferase reaction.
Date: December 1984
Creator: Hara, Shinichi

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 dimerization while 33% are formed by silenoid coupling. In hexane the order of reactivity for addition, t-Bu > sec-Bu > n-Bu, is opposite that for fluorine substitution. The vinyl substitution is most significant with secondary alkyllithium reagents including the tert-butyllithium adduct to dimethylfluorovinylsilane and with sec-butyllithium itself. Evidence for the formation of vinyllithium or ethylene in the process could not be obtained.
Date: August 1985
Creator: Cheng, Albert Home-Been

A Study of the Processing Properties of Hard-Particle Reinforced Composite Solders

Description: The microstructural, mechanical and thermal properties of various composite solder formulations were investigated. Special interest was given in observing the processing properties, microstructural characteristics, fatigue behavior, tensile strength, and the effect of environmental ageing on the composite solder formulations. The solderability parameters wetting and speed of soldering, reflow temperature, and the thermal stability of the resulting composite solder were also examined.
Date: May 1994
Creator: Calderon, Jose Guadalupe

Substituent Effects: A Computational Study on Stabilities of Cumulenes and Low Barrier Hydrogen Bonds

Description: The effect of substituents on the stabilities of cumulenes-ketenes, allenes, diazomethanes and isocyanates and related systems-alkynes, nitriles and nitrile oxides is studied using the density functional theory (B3LYP, SVWN and BP86) and ab initio (HF, MP2) calculations at the 6-31G* basis set level. Using isodesmic reactions, correlation between stabilization energies of cumulenes and substituent group electronegativities (c BE) is established and the results from DFT and MP2 methods are compared with the earlier HF calculations. Calculations revealed that the density functional methods can be used to study the effect of substituents on the stabilities of cumulenes. It is observed that the cumulenes are stabilized by electropositive substituent groups from s -electron donation and p -electron withdrawal and are destabilized by electronegative substituent groups from n-p donation. The calculated geometries of the cumulenes are compared with the available experimental data.High level ab initio and density functional theory calculations have been used to study the energetics of low-barrier hydrogen bond (LBHB) systems. Using substituted formic acid-formate anion complexes as model LBHB systems, hydrogen bond strength is correlated to the pKa mismatch between the hydrogen bond donor and the hydrogen bond acceptor. LBHB model systems are characterized by the 1H-NMR chemical shift calculations. A linear correlation between the calculated hydrogen bond strength and the predicted 1H-NMR chemical shift was established. It is concluded that the pKa matching within the enzyme active site of the two species involved in the LBHB is important to maximizing catalytic stabilization.
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Date: August 2000
Creator: Kumar, Ganesh Angusamy

Substitution Chemistry of the Cobalt Complexes [Co₂(CO)₆(PhC≡CR) (R=Ph, H) and PhCCo₃(CO)₉] with the Diphosphine Ligands [Bis(diphenylphosphino)maleic Anhydride (BMA) and (Z)-Ph₂PCH=CHPPh₂]. Reversible Chelate-to-Bridge Diphosphine Ligand Exchange, Phosphorus-Carbon Bond Cleavage and Phosphorus-Carbon Bond Formation

Description: The tricobalt cluster PhCCo3(CO)9 (1) reacts with the bidentate phosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in the presence of added Me3NO to give the diphosphine-substituted cluster PhCCo3(CO)7(bma) (2). Cluster 2 is unstable in solution, readily losing CO to afford Co3(CO)6[(μ2-η2/η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ2-PPh2) (3) as the sole observed product. VT-31P NMR measurements on cluster 2 indicate that the bma ligand functions as both a chelating and a bridging ligand. At -97 °C, 31P NMR analysis of 2 reveals a Keq of 5.7 in favor of the bridging isomer. The bridged bma cluster 2 is the only observed species above -50°C. The solid-state structure of 2 does not correspond to the major bridging isomer observed in solution but rather the minor chelating isomer. The conversion of 2 to 3 followed first-order kinetics, with the reaction rates being independent of the nature of the reaction solvent and strongly suppressed by added CO, supporting a dissociative loss of CO as the rate-determining step. The activation parameters for CO loss were determined to be ΔH≠ = 29.9 ± 2.2 kcal/mol and ΔS≠ = 21.6 ± 6 eu.
Date: December 1994
Creator: Yang, Kaiyuan

Sulfur-induced Corrosion at Metal and Oxide Surfaces and Interfaces

Description: Sulfur adsorbed on metallic and oxide surfaces, whether originating from gaseous environments or segregating as an impurity to metallic interfaces, is linked to the deterioration of alloy performance. This research dealt with investigations on the interactions between sulfur and iron or iron alloy metallic and oxide surfaces under ultrahigh vacuum conditions. Sulfur was either intentionally dosed from a H2S source on an atomically clean metal surface, or segregated out as an impurity from the bulk to the metal surface by annealing at elevated temperatures.
Date: August 1997
Creator: Cabibil, Hyacinth (Hyacinth Liesl)

Surface and Interfacial Studies of Metal-Organic Chemical Vapor Deposition of Copper

Description: The nucleation and successful growth of copper (Cu) thin films on diffusion barrier/adhesion promoter substrates during metal-organic chemical vapor deposition (MOCVD) are strongly dependent on the initial Cu precursor-substrate chemistry and surface conditions such as organic contamination and oxidation. This research focuses on the interactions of bis(1,1,1,5,5,5-hexafluoroacetylacetonato)copper(II), [Cu(hfac)2], with polycrystalline tantalum (Ta) and polycrystalline as well as epitaxial titanium nitride (TiN) substrates during Cu MOCVD, under ultra-high vacuum (UHV) conditions and low substrate temperatures (T < 500 K). The results obtained from X-ray photoelectron spectroscopy (XPS), Auger Electron Spectroscopy (AES) and Temperature Programmed Desorption (TPD) measurements indicate substantial differences in the chemical reaction pathways of metallic Cu formation from Cu(hfac)2 on TiN versus Ta surfaces.
Date: December 1997
Creator: Nuesca, Guillermo M.

Syntheses of Antimetabolites

Description: In these studies several different types of antimetabolites were synthesized, and their biological effects were examined in various assay systems. More extensive investigations were done in microbial systems in which many of the compounds proved to be inhibitory to growth, and attempts were made to determine the mode of biochemical action by adding supplements of the appropriate natural metabolite.
Date: January 1970
Creator: Clifton, George Gil

Syntheses of Highly Strained Energetic Molecules and Development of New Synthetic Methodology

Description: The objective of this study was to synthesize new energetic, strained, saturated polycyclic compounds. For this purpose, new methodology has been developed, as follows: (i) Ketenes have been generated in situ via treatment of aldo-, keto- or alkenoic acid with either toluenesulfonyl chloride or 2-chloro-1-methylpyridfniurn iodide (Mulkaiyama's reagent). The reactive intermediates thereby generated have been found to undergo intramolecular [2+2] cycloaddition reactions in these systems.
Date: May 1987
Creator: Wu, An-hsiang

Synthesis and Characterization of Copper(II) Complexes

Description: A series of dihydroxy bridged copper(II) complexes of the type [(L)Cu(OH)₂Cu(L)]x₂ * nH₂0, where L is 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine or 1,10-phenanthroline, x is a counter ion, and n is the number of water molecules, was synthesized. In the case of monohydroxy bridged copper(II) complexes, we have found a new method of synthesis for [ (L)₂Cu(OH)Cu(L)₂ ] (ClO₄)₃, where L is 2,2'-bipyridine or 1,10-phenanthroline. We have synthesized five new monohydroxy bridged copper(II) complexes, thus increasing the number of monohydroxy bridged copper(II) complexes to nine. All complexes have been characterized by infrared spectroscopy, UV-visible spectroscopy, magnetic moments, and elemental analysis. The electron spin resonance results establish that the fulvic acids contain organic free radicals as an internal part of their molecular structure. The concentration of unpaired electrons will increase by increasing the pH. The unpaired electron in fulvic acid interacts with the unpaired electron on copper(II) through the Π system, and this will decrease the spin concentration of fulvic acid complexed with copper(II). The displacement of titration curve from a free ligand (fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phospherine, phosphothreonine, and 3-phosphoglyceric acid, to a ligand plus copper(II) (1:1 ratio) shows there is a strong interaction between copper(II) and the corresponding ligand. All complexes absorb UV-visible at 250-300 nm. The absorption intensity changes as a function of pH. Copper (II) forms a complex with fructose-1,6-diphosphate, ribulose-1,5-diphosphate, phosphoserine, phosphothreonine, and 3-phosphoglyceric acid by the ratio of 1:3, 1:3, 1:1, 1:1, and 1:2, respectively.
Date: December 1984
Creator: Amani, Saeid