UNT Libraries - 164 Matching Results

Search Results

Mechanisms of Methoxide Ion Substitution and Acid- Catalyzed Z/E Isomerization of N-Methoxyimines

Description: The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] reveal an element effect for the Z isomers of Br:Cl:F(1e) = 2.21:1.00:79.7 and for the E isomers of Cl:F(2e) = 1.00:18.3. With the p-OCH3-imidoyl halides the following element effects are found: Br:Cl:F(1h) = 2.78:1.00:73.1 for the Z isomer and Br:Cl:F(2h) = 1.97:1.00:12.1 for the E isomer. Measurement of activation parameters revealed ∆S≠ = -17 eu for 1e and ∆S≠ = -9.9 eu for 2e. Ab initio calculations (HF/6-31+G*, MP2/6-31+G*//HF/6-31+G*, B3LYP/6- 31+G*//HF/6-31+G*, HF-SCIPCM/6-31+G*//HF/6-31+G*) were performed to define the reaction surface. These calculations demonstrate a relatively large barrier for nucleophilic attack in relation to halogen loss and support the experimental findings that this reaction proceeds by an addition-elimination mechanism (AN# + DN). The imidoyl fluorides have been used to synthesize highly functionalized O-methyloximes by reaction with enolate anions derived from malononitrile, ethyl cyanoacetate, and diethyl malonate. Acid-catalyzed isomerization of compounds containing the O-methyloxime moiety have been investigated with ab initio calculations (HF/6-31+G*, MP2/6- 31+G*//HF/6-31+G*, B3LYP/6-31+G*//HF/6-31+G*). Barriers for rotation around the C-N bond following protonation have been calculated. The calculated barriers are discussed in relation to an isomerization mechanism of protonation-rotation versus a nucleophilic catalysis.
Access: This item is restricted to UNT Community Members. Login required if off-campus.
Date: December 2001
Creator: Dolliver, Debra D.

Metal-Aluminum Oxide Interactions: Effects of Surface Hydroxylation and High Electric Field

Description: Metal and oxide interactions are of broad scientific and technological interest in areas such as heterogeneous catalysis, microelectronics, composite materials, and corrosion. In the real world, such interactions are often complicated by the presence of interfacial impurities and/or high electric fields that may change the thermodynamic and kinetic behaviors of the metal/oxide interfaces. This research includes: (1) the surface hydroxylation effects on the aluminum oxide interactions with copper adlayers, and (2) effects of high electric fields on the interface of thin aluminum oxide films and Ni3Al substrate. X-ray photoelectron spectroscopy (XPS) studies and first principles calculations have been carried out to compare copper adsorption on heavily hydroxylated a- Al2O3(0001) with dehydroxylated surfaces produced by Argon ion sputtering followed by annealing in oxygen. For a heavily hydroxylated surface with OH coverage of 0.47 monolayer (ML), sputter deposition of copper at 300 K results in a maximum Cu(I) coverage of ~0.35 ML, in agreement with theoretical predictions. Maximum Cu(I) coverage at 300 K decreases with decreasing surface hydroxylation. Exposure of a partially dehydroxylated a-Al2O3(0001) surface to either air or 2 Torr water vapor results in recovery of surface hydroxylation, which in turn increases the maximum Cu(I) coverage. The ability of surface hydroxyl groups to enhance copper binding suggests a reason for contradictory experimental results reported in the literature for copper wetting of aluminum oxide. Scanning tunneling microscopy (STM) was used to study the high electric field effects on thermally grown ultrathin Al2O3 and the interface of Al2O3 and Ni3Al substrate. Under STM induced high electric fields, dielectric breakdown of thin Al2O3 occurs at 12.3 } 1.0 MV/cm. At lower electric fields, small voids that are 2-8 A deep are initiated at the oxide/metal interface and grow wider and deeper into the metal substrate, which eventually leads to either physical collapse or dielectric ...
Date: December 2001
Creator: Niu, Chengyu

Metal Complexes of 2,3-Quinoxalinedithiol

Description: A series of new planar complexes with the dianion of 2,3-quinoxalinedithiol ligand has been prepared. The complexes have been characterized from the study of their analyses, magnetic moment, conductance, polarograms, electron spin resonance spectra, and electronic spectra, and compared with the available data on the corresponding maleonitriledithiolene and toluene-3,4-dithiolene complexes.
Date: May 1969
Creator: Ganguli, Kalyan Kumar, 1912-

Metal (II) Complexes with N-Salicylideneamino Acids

Description: Transition metal complexes derived from Schiff bases have rendered an important contribution to the development of modern coordination chemistry. Various stable compounds have been prepared having synthetic, biological, and physicochemical interest. In particular, complexes of salicylaldimines, B-ketoamines, and closely related ligand systems have been investigated.
Date: August 1969
Creator: Carlisle, Gene Ozelle

Metallization and Modification of Low-k Dielectric Materials

Description: Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity toward aluminum chemical vapor deposition. Silicon-carbon (Si-Cx) films were formed by electron beam bombardment of trimethylvinylsilane films which were adsorbed onto metal substrates at low temperatures in ultra-high vacuum. Oxygen was also added to the films by coadsorbing water before electron beam bombardment; the films were stable to more than 700 K, with increasing silicon-oxygen bond formation at elevated temperatures. Copper metal was sputter deposited in small increments onto non-oxygenated films. X-ray photoelectric spectra show three-dimensional copper growth (rather than layer-by-layer growth), indicating only weak interaction between the copper and underlying films. Annealing at elevated temperatures caused coalescence or growth ...
Date: December 2008
Creator: Martini, David M.

Methods Development for Ion Chromatography

Description: Ion chromatography (IC) as developed by Small et. al. in 1975 has become an efficient and reliable analytical technique for simultaneous analysis of multiple ions in solution. The principle requirement prior to use the IC for an analysis is sample preparation; these include sample decomposition, solvent extraction, and trapping in case the target element is in the gas phase, etc. Solvent extractions for fluoride, chloride, sodium, ammonium, and potassium ions which are soluble in soils are described. Sample decompositions include silicate rocks using hydrofluoric acid for the determination of phosphorus; organic pesticides using lithium fusion technique for the determination of halide and cyanide ions are also described. After these sample preparation techniques, the aqueous solutions obtained were analyzed on the ion chromatograph for the analyses of the anions and cations mentioned above. Recovery and reproducibility of each technique is in general quite good and the comparison between the results obtained from the IC method and other instrumentation are given.
Date: May 1986
Creator: Supachai Maketon

Microwave-Assisted Synthesis and Photophysical Properties of Poly-Imine Ambipolar Ligands and Their Rhenium(I) Carbonyl Complexes

Description: The phenomenon luminescence rigidochromism has been reported since the 1970s in tricarbonyldiimine complexes with a general formula [R(CO)3LX] using conventional unipolar diimine ligands such as 2,2;-bipyridine or 1,10-phenanthroline as L, and halogens or simple solvents as X. As a major part of this dissertation, microwave-assisted synthesis, purification, characterization and detailed photoluminescence studies of the complex fac-[ReCl(CO)3L], 1, where L = 4-[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl]-N,N-diethylbenzenamine are reported. The employment of microwaves in the preparation of 1 decreased the reaction time from 48 to 2 hours compared to the conventional reflux method. Stoichiometry variations allows for selective preparation of either a mononuclear, 1, or binuclear, fac-[Re2Cl2(CO)6], 2, complex. The photophysical properties of 1 were analyzed finding that it possesses significant luminescence rigidochromism. The steady state photoluminescence emission spectra of 1 in solution shift from 550 nm in frozen media to 610 nm when the matrix becomes fluid. Moreover, a very sensitive emission spectral analysis of 0.1 K temperatures steps shows a smooth transition through the glass transition temperature of the solvent host. Furthermore, synthetic modifications to L have attained a family of ambipolar compounds that have tunable photophysical, thermophysical and other material properties that render them promising candidates for potential applications in organic electronics and/or sensors - either as is or for their future complexes with various transition metals and lanthanides.
Access: This item is restricted to UNT Community Members. Login required if off-campus.
Date: August 2017
Creator: Salazar Garza, Gustavo Adolfo

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 calculated from the bend) and (C-Br stretch) lineshapes are of the same magnitude in CI^B^. The vibrational dephasing time of [C-D(H) stretch] is twice as long in CD2Cl2 as in CH-^C^, and the relaxation time of (C-Cl stretch) is greater in CI^C^ than in CD2CI2. Isotropic relaxation times for all three stretching vibrations are significantly shorter in C^BrCl than in CI^C^ or CI^B^. Application of the Kubo model revealed that derived modulation times are close to equal for equivalent vibrations in the various dihalomethanes. Thus, the more efficient relaxation of the A^ modes in CE^BrCl can be attributed almost entirely to the broader mean squared frequency perturbation of the vibrations in this molecule.
Date: May 1985
Creator: Chen, Jen Hui

Molecular Dynamics in the Liquid Phase by FT-NMR, FT-IR and Laser Raman Lineshape Analysis

Description: Nuclear magnetic resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids because nuclear spin-lattice relaxation times are dependent upon the details of molecular motion. The combined application of Raman and Infrared (IR) lineshape analysis can furnish more complete information to characterize the anisotropic rotation of molecules. Presented here are the studies of NMR relaxation times, together with Raman/IR Mneshape analysis of the solvent and temperature dependence of rotational diffusion in 1,3,5-tribromobenzene and 1,3,5-trifluorobenzene. In these experiments, it was found that the rotational diffusion constants calculated from Perrin's stick model were two to three times smaller than the measured values of D, and D,,. Similarly, rotational diffusion constants predicted by the Hu-Zwanzig slip model were too large by a factor of 2. Application of the newer Hynes-Kapral-Weinberg model furnished rotational diffusion constants that were in reasonable agreement with the experimental results. The vibrational peak frequencies and relaxation times of the isotropic Raman spectra of the υ1 modes of CD2Br2 and CHBr3 were studied in solution. The frequency shifts in non-interactive solvents were explained well on the basis of solution variations in the dispersion energy. In Lewis bases, the displacements were in some, but not all, cases greater than predicted. On the other hand, it was found that the vibrational relaxation times of the C-H/C-D modes decreased dramatically in all Lewis base solvents. Therefore, it was concluded that relaxation times of the υ1 modes, rather than frequency shifts, furnish a more reliable measure of hydrogen bonding interactions of halomethanes in solution.
Date: August 1988
Creator: Chen, Fu-Tseng Andy

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 interaction with Lewis bases (= L, alkylphosphines and alkyl phosphites) for the Cs intermediates and via bimolecular interaction of L with the C4v intermediates, together with activation parameters for these processes have been determined. The rates of interactions at the Cs intermediates are significantly faster than at the C4v intermediates.
Date: May 1986
Creator: Mansour, Saber E. (Saber El-Sayed)

An NMR study of 2-ethyl-1-butyllithium and of 2-ethyl-1-butyllithium/lithium 2-ethyl-1-butoxide mixed aggregates

Description: A 1H, 13C, and 6Li NMR study of 2-ethyl-1-butyllithium indicated that 2-ethyl-1-butyllithium exists only as a hexameric aggregate over the entire temperature range of 25 to - 92.1 ° C in cyclopentane. Reacting 2-ethyl-1-butyllithium with 2-ethyl-1-butanol resulted in alkyllithium/lithium alkoxide mixed aggregates, apparently of the form Ra(RO)bLia+b. A multinuclear, variable temperature NMR study of samples with O:Li ratios of 0.2 and 0.4 showed, in addition to the alkyllithium, the formation of four mixed aggregates, one of them probably an octamer. Higher O:Li ratio samples showed the formation of several other mixed aggregates. Mixing 2-ethyl-1-butyllithium with independently prepared lithium 2-ethyl-1-butoxide formed the same mixed aggregates formed by in situ synthesis of lithium alkoxide. Lithium 2-ethyl-1-butoxide also exists as aggregates in cyclopentane.
Date: May 2001
Creator: Ferreira, Aluisio V. C.

NMR Study of the Reorientational and Exchange Dynamics of Organometallic Complexes

Description: Investigations presented here are (a) the study of reorientational dynamics and internal rotation in transition metal complexes by NMR relaxation experiments, and (b) the study of ligand exchange dynamics in transition metal complexes by exchange NMR experiments. The phenyl ring rotation in Ru3(CO)9(μ3-CO)(μ3-NPh) and Re(Co)2(CO)10(μ3- CPh) was monitored by 13C NMR relaxation experiments to probe intramolecular electronic and/or steric interactions. It was found that the rotation is relatively free in the first complex, but is restrained in the second one. The steric interactions in the complexes were ascertained by the measurement of the closest approach intramolecular distances. The rotational energy barriers in the two complexes were also calculated by using both the Extended Hiickel and Fenske-Hall methods. The study suggests that the barrier is due mainly to the steric interactions. The exchange NMR study revealed two carbonyl exchange processes in both Ru3(CO)9(μ3-CO)(μ3-NPh) and Ru3(CO)8(PPh3)(μ3-CO)(μ3-NPh). The lower energy process is a tripodal rotation of the terminal carbonyls. The higher energy process, resulting in the exchange between the equatorial and bridging carbonyls, but not between the axial and bridging carbonyls, involves the concerted formation of edge-bridging μ2-CO moieties. The effect of the PPh3 ligand on the carbonyl exchange rates has been discussed. A combination of relaxation and exchange NMR found that PPh3 ligand rotation about the Ru-P bond is slow on the exchange NMR time scale and the phenyl rotation about the P-Cipso bond is fast on the exchange NMR time scale but is slow on the NMR relaxation time scale.
Date: May 1996
Creator: Wang, Dongqing

Nuclear Magnetic Resonance Spectra of Some 1,2,4-triazoles

Description: In the work undertaken here, NMR has been used to ascertain the structure of some 1,2,4-triazoles. The investigation provides information concerning the structure of potentially tautomeric triazoles such as hydroxy- and aminotriazole. Connected with this aspect of triazole chemistry is the larger problem of mesohydric tautomerism. The present study also yields information for a comparison of substituent effects in triazoles, N-heteroaromatic substances and benzene.
Date: January 1967
Creator: Creagh, Linda Truitt

Ozonolysis and Cycloaddition Reaction of (Trimethylsilyl)ketene

Description: The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.
Date: August 1980
Creator: Saidi, Kazem

Part 1. Investigation of Aluminum Amino Acid Complexes; Part 2. Structural Studies of Aluminum Chalcogen Bonds

Description: Five different complexes of aluminum and amino acids have been synthesized and characterized. Reaction between aluminum halides and amino acids that do not contain either a carboxylate or a hydroxy group in the side chain produce complexes of the general formula, [Al(amino acid)_n(halide)_3-n]_m. The most prevalent form of this form of complex is where n = 2, and an example of this in which the halide is replaced by hydroxide ligand has been structurally characterized. The complex for which n = 3 may be obtained by employing a large excess of acid, and that for which n = 1 may be obtained by employing either equimolar conditions or an excess of aluminum halide. Reactions of aluminum halides with amino acids that contain either a carboxylate or hydroxy-containing side chain may result in complexes in which the side-chain is also bound. These proved impossible to characterize fully in the case of aspartic acid. For serine, however, a complex in which the amino acid binds in a chelating fashion through both the carboxylate and hydroxy groups was isolated. It was possible to form complexes when utilizing aluminum alkyls as the metal source. However, these complexes could only be isolated when the reactivity of the species was controlled by the presence of bulky groups. In these cases, the monomeric R_2Al(amino acid) complexes were obtained. Four complexes that contain aluminum-chalcogen bonds were structurally characterized. These included the bulky alkoxide complexes (BHT)_2AIH(OEt_2), (BHT)_3Al(cyclohexanone), and the cubane [(t-amyl)AlS]_4.
Date: May 1996
Creator: Gravelle, Philip W. (Philip Wyn)

Part I: Solid State Studies of Larger Calixarenes : Part II: Synthesis and Characterization of Metallocalixarenes

Description: Calixarenes are a class of macrocyclic compounds that have garnered interest in large part because of their ability to form host-guest complexes with various types of molecules. For all of the studies of complex formation by calixarenes, most of the work to date has concentrated upon the smaller calixarenes, and little is understood about the relationship between the complexes formed when in solution and that observed in the solid state. The first part of the study, presented in Chapter 3, is of the solid-state properties of two of the larger calixarenes, and in comparison to other reported structures reveals patterns to the observed conformations both in the solid state and in solution. The formation of metal complexes has also been investigated and has focused extensively upon the metals as guests. Thus, the ability of the calixarenes to act as ligands in inorganic complexes has been virtually untapped, despite the polyoxo binding site they can easily provide, and very few metallocalixarenes have been reported. The second part of this study goes beyond the simple solid-state properties of such compounds, and involves the synthesis of several metallocalixarenes as part of a project directed at the functionalization of calixarenes with the components of a class of catalysts known to polymerize various olefins. These catalysts, commonly referred to as Ziegler-Natta catalysts, are introduced in Chapter 4. The new compounds presented here--three new aluminocalixarenes in Chapter 5 and a new titanocalixarene in Chapter 6--were synthesized so as to contain some of the same components observed in several of the other catalysts. These new compounds have been characterized crystallographically as well as through proton and multinuclear NMR, and observed conformational patterns are discussed.
Date: May 1998
Creator: Smith, Janna Marie

The performance of density functional theory with the correlation consistent basis sets.

Description: Density functional theory has been used in combination with the correlation consistent and polarization consistent basis sets to investigate the structures and energetics for a series of first-row closed shell and several second-row molecules of potential importance in atmospheric chemistry. The impact of basis set choice upon molecular description has been examined, and irregular convergence of molecular properties with respect to increasing basis set size for several functionals and molecules has been observed. The possible reasons and solutions for this unexpected behavior including the effect of contraction and uncontraction, of the basis set diffuse sp basis functions, basis set superposition error (BSSE) and core-valence sets also have been examined.
Date: August 2005
Creator: Wang, Xuelin

Phosphorescent Emissions of Coinage Metal-Phosphine Complexes: Theory and Photophysics

Description: The major topics discussed are all relevant to the bright phosphorescent emissions of coinage metal complexes (Cu(I), Ag(I) and Au(I)) with an explanation of the theoretical background, computational results and ongoing work on the application in materials and optoelectronic devices. Density functional computations have been performed on the majority of the discussed complexes and determined that the most significant distortion that occurs in Au(I)-phosphine complexes is a near and beyond a T-shape within the P-Au-P angle when the complexes are photoexcited to the lowest phosphorescent excited state. The large distortion is experimentally qualified with the large Stokes' shift that occurs between the excitation and emission spectra and can be as large as 18 000 cm-1 for the neutral Au(I) complexes. The excited state distortion has been thoroughly investigated and it is determined that not only is it pertinent to the efficient luminescence but also for the tunability in the emission. The factors that affect tunability have been determined to be electronics, sterics, rigidity of solution and temperature. The luminescent shifts determined from varying these parameters have been described systematically and have revealed emission colors that span the entire visible spectrum. These astounding features that have been discovered within studies of coinage metal phosphorescent complexes are an asset to applications ranging from materials development to electronics.
Date: December 2009
Creator: Sinha, Pankaj

Picosecond Spectroscopy of Rhodamine B

Description: A series of picosecond excite-probe experiments was performed on various concentrations of aqueous and ethanolic solutions of rhodamine B in order to determine the existence of dimerization in those solutions. The goals of the research presented in this dissertation were twofold. Initially, various techniques of time-resolved spectroscopy were to be employed to further characterize the ground and excited-state molecular properties of the aqueous RB dimer. The information obtained, and the techniques developed in that study would then be utilized in an effort to secure evidence which would support or refute the claims of rhodamine B dimerization in an ethanolic solution.
Date: December 1981
Creator: Clark, James Burton

Precipitation and Pattern Formation under Far-From-Equilibrium Conditions

Description: Precipitates of a series of alkaline earth metal (barium and strontium) carbonates, chromates, phosphates, and sulfates were formed at high supersaturation by diffusion through silica hydrogel, agarose hydrogel, and the freshly developed agarosesilica mixed gels. The reaction vessels could be a small test tube, a recently designed standard micro slide cassette and a enlarged supercassette. Homogeneous nucleation is thought to have taken place, and particle development led to the formation of an unusual category of materials, known as Induced Morphology Crystal Aggregates [IMCA], at high pH under far-from-equilibrium conditions. Standard procedures were developed in order to produce homogeneous gels. Particle development led to characteristic style of pattern formation, which I have called monster, spiral, and flake. Among these IMCA, barium carbonate, chromate, and sulfate were moderately easy to grow. Barium phosphate was very difficult to grow as IMCA due to formation of poorly crystalline spherulites. IMCA of strontium carbonate, chromate and sulfate could be developed at high basic pH in the presence of silicate. Strontium carbonate sheet morphology displays a unique property, double internal layer structure, which was identified by backscattering electron imaging (BEI). Selected electron diffraction (SAD) revealed a new crystal phase which was called "Dentonite". Precipitate particles were isolated using a non-destructive isolation technique. Optical microscopy was widely used to examine particles in situ and scanning electron microscopy and X-ray dispersive energy (EDX) spectroscopy were applied to particles ex situ, together with ESCA for surface analysis. Growth patterns were found to be strongly dependent on pH. Other related pattern formation processes were also investigated including normal and dendritic structures, spherulitic structures and periodic pattern formation. Some interpretations were proposed in terms of mechanism. Chemical additive effects were examined experimentally in the calcium phosphate system. The effect of external ionic strength was investigated, and it was found that a ...
Date: August 1995
Creator: Chen, Peng, 1960-

Predicting Chemical and Biochemical Properties Using the Abraham General Solvation Model

Description: Several studies were done to illustrate the versatillity of the Abraham model in mathematically describing the various solute-solvent interactions found in a wide range of different chemical and biological systems. The first study focused on using the solvation model to construct mathematical correlations describing the minimum inhibitory concentration of organic compounds for growth inhibition towards the three bacterial strains Porphyromonas gingivalis, Selenomonas artemidis, and Streptococcus sobrinus. The next several studies expand the practicallity of the Abraham model by predicting free energies of partition in chemical systems. The free energy studies expand the use of the Abraham model to other temperatures and properties by developing correlations for the enthalpies of solvation of gaseous solutes of various compounds dissolved in water, 1-octanol, hexane, heptane, hexadecane, cyclohexane, benzene, toluene, carbon tetrachloride, chloroform, methanol, ethanol, 1-butanol, propylene carbonate, dimethyl sulfoxide, 1,2-dichloroethane, N,N-dimethylformamide, tert-butanol, dibutyl ether, ethyl acetate, acetonitrile, and acetone. Also, a generic equation for linear alkanes is created for use when individual datasets are small. The prediction of enthalpies of solvation is furthered by modifying the Abraham model so that experimental data measured at different temperatures can be included into a single correlation expression. The temperature dependence is directly included in the model by separating each coefficient into an enthalpic and entropic component. Specifically, the final study describes the effects of temperature on the sorption coefficients of organic gases onto humic acid. The derived predicted values for each research study show a good correlation with experimental values.
Date: May 2009
Creator: Mintz, Christina

Preparation and Stereochemistry of Reactive Intermediates Containing a Silicon-Carbon Double Bond

Description: 1,1-Dimethyl-2-neopentylsilene reacted with the N-methylimine of benzophenone to give 1,2,2-trimethyl-3- neopentyl-4,4-diphenyl-l-aza-2-silacyclobutane, I, and 2,3,4,4a-tetrahydro-2,3,3-trimethyl-1-phenyl-4-neopentyl-2- aza-3-silanephthalene, II, in 35% and 20% yields, respectively. Compounds I and II did not serve as thermal silene precursors. Heating I and II to over 280°C did not yield 1,3-disilacyclobutanes. In the presence of 2,3- dimethyl-1,3-butadiene typical silene products were not obtained. However, I and II reacted rapidly with methanol at room temperature to give the ring-opened products (E)-2- methoxy-2,5,5-trimethyl-2-silahex-3-ene, III, 1,1- diphenyldimethylamine, IV, and 2-methoxy-2,5,5-trimethyl-3- (N-methylaminodiphenyl) methyl-2-silahexane, V.
Date: December 1991
Creator: Uang, Shinian

Preparation of flat dendrimers and polycyclic aromatic hydrocarbons connected via 1,3,5-triethynylbenzene core.

Description: Flat dendrimers, consisting of a hexavalent aromatic core and rigid ethynyl units locked in place by ether connections were developed based upon the divergent synthetic method. Alternating functional groups were adopted on each site of the hexa-substituted benzene, in order to avoid undesired cyclization pathways. The flat structures of conjugated dendrimers would allow investigation on the discotic liquid crystal properties. In addition, these ethylnyl dendrimers are expected to show directed energy and electron transfer with a highly conjugated system, and thus are effective in the preparation of photoreactive materials such as electronic sensors or light harvesting materials. Conjugated polycyclic aromatic hydrocarbons, consisting of naphthalene, anthracene, pyrene, and phenanthrene groups connected via 1,3,5-triethynylbenzene cores, were synthesized. These molecules exhibited luminescence properties and the π-complexation with a mercury trifunctional lewis acid are expected to enhance the phosphorescence in the presence of the heavy metal due to the spin-orbit coupling. Besides, owing to the presence of heavy metal atom in the Au (I) complexes linked by s-bonded triethynyltriphenylene luminophore, the phosphorescence occurs from a metal-centered emission. The conjugated organic luminophores have been developed to produce excellent quantum efficiencies, brightness, and long lifetimes.
Date: December 2008
Creator: Jung, Jiyoung