The objective of this research problem was to synthesize aldohaloketenes and investigate the chemistry of this new class of ketenes.

This dissertation is a study involving the synthesis and chemistry of arylhaloketenes and cyclopentadiene cycloadducts, and a study of the cycloadduct isomer distribution was begun.

This study is concerned with certain factors affecting the content of lactobacillic acid in Lactobacillus plantarum. Three main areas of investigation are reported herein. The effects of both the oxygen tension and the pH of the culture medium on the accumulation of lactobacillic acid were determined. In addition, monolayer studies were conducted to determine the influence of cyclopropane fatty acid content on the molecular packing of membrane lipids.

This thesis is an investigation of the vacuum uv spectra of the phosphorus, phosphoryl, and thiophosphoryl trichlorofluorides in the region 1250 to 3000A. Assignments for absorption bands are made utilizing results from photoelectron spectra and ab initio calculations, oscillator strengths for absorption bands, and CNDO/2 molecular orbital calculations. Results from CNDO/2 calculations are compared with theoretical calculations, and experimental data are discussed with regard to the bonding in the compounds.

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.

The oxidative elimination reactions of (5-X-phen)Mo(C0)₄ (X = H, CH₃, Cl, NO₂; phen = o-phenanthroline) and (3,4,7,8-(CH₃)₄-phen)Mo(CO)₄ with mercuric chloride in acetone have been investigated. In these reactions, a carbon monoxide group is replaced by two univalent ligands, accompanied by the corresponding increase in coordination number and formal oxidation state of the central metal atom, to give products of the type, (X-phen)Mo(CO)₃(Cl)HgCl. With the exception of (3,4,7,8-(CH₃)₄-phen), the substituted o-phenanthrolines were selected so as to minimize steric differences from one substrate to another while obtaining the widest range of pKₐ of the ligand.

A study was conducted to investigate the relationships between cybergaming treatment groups and the control group (N = 99: ncontrol = 8; nlogic = 29; nspatial = 30; ncombination = 32) with success in the organic chemistry I course as measured by achievement over a 10-week period. The treatment groups included logic training, spatial training, and combination logic-spatial training. Students' ability was measured by pre/post exams using the Group Assessment of Logical Thinking (GALT) to measure logic ability, Purdue Visualizations of Rotations (ROT) test to measure spatial skills, and the General-Organic-Biochemistry (GOB) Exam to measure content attainment. Finally, students' responses about participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. A second study was conducted to evaluate the relationship between the cybergaming treatment and control groups (N = 88: nexperimental = 27; ncontrol = 61) with success in the general chemistry I course as measured by achievement and final course averages and grades. The cybergaming treatment group underwent intensive combination logic-spatial training for 10 weeks. Students' progress was measured using three pre/post instruments: Group Assessment of Logical Thinking (GALT) measured logic ability, Purdue Visualizations of Rotations (ROT) Test measured spatial skills, and the California …

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.

Within this educational endeavor instrumental development was explored through the investigation of microwave induce stable electromagnetic waves within a non-linear yttrium iron garnet ferromagnetic waveguide. The resulting magnetostatic surface waves were investigated as a possible method of rapid analytical evaluation of material composition. Initial analytical results indicate that the interaction seen between wave and material electric and magnetic fields will allow phase coherence recovery andanalysis leading to enhancement of analytical value. The ferromagnetic waveguide selected for this research was a high quality monocrystalline YIG (yttrium iron garnet) film. Magnetostatic spin waves (MSW) were produced within the YIG thin waveguide. Spin waves with desired character were used to analytically scan materials within the liquid and solid phase.

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, …

Polymeric nanoparticles were synthesized and loaded with Cu²⁺ to explore the therapeutic potential for catically active transition metal ions and complexes other than cisplatin. Two types of nanoparticles were synthesized to show the potential for polymer based vectors. Copper loading and release were characterized via inductively coupled plasma mass spectrometry (ICP MS), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis. Results demonstrated that Cu could be loaded to the nano-sized carriers in an aqueous environment, and that the release was pH-dependent. The toxicity of these particles was measured in HeLa cells where significant toxicity was observed in vitro via dosing of high Cu-loaded nanoparticles. No significant toxicity was observed in cells dosed with Cu-free nanoparticles.

Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models …

This thesis describes the synthesis and preliminary enzymatic study of glutaryl-S-(8-aminooctyl)-L-cysteinylglycine and glutaryl-S-(10-aminodecyl)-L-cysteinylglycine as inhibitors of glyoxalase I. These analogs of glutathione were prepared as potential ligands for affinity chromatography purification of glyoxalase I. The compounds were synthesized by a seven-step procedure in overall yields of 24% for the octyl analog and 33% for the decyl analog. Both compounds exhibited mixed type inhibition of the enzyme, with the decyl derivative being more inhibitory than the octyl derivative. The inhibition was nonlinear (parabolic) for both compounds. Although less inhibitory than the corresponding S-substituted glutathione derivatives, these analogs are promising candidates for affinity chromatography ligands. Such compounds may also be useful in studying the mechanism of glyoxalase I.

The three-dimensional x-ray structure of 2,2'-bipyridylglycinatochloro copper(II) dihydrate has been fully refined to a final R factor of 0.081. The bipyridyl and glycine ligands are arranged about the central copper atom in a square planar configuration while the chlorine atom is 2.635 angstroms above this plane directly over the copper atom. This unusually long distance is explained by the positioning of a glycine group on the opposite side of the square plane, resulting in a distorted octahedral arrangement. Also, the chlorine atom is linked to three oxygen atoms via hydrogen bonding, thus stabilizing the distorted octahedral complex.

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.

Slag, by itself, shows very little hydraulic activity. However, hydration is greatly accelerated by incorporation of the slag with Portland cement. This phenomenon is due to the activating role of calcium hydroxide released from the hydration of Portland cement. This study was aimed at finding other activators that will increase hydration in both synthetic and commercial slags. The effects of chemical composition and the aggregation state of the slag on the hydration process were also investigated. For the synthetic slags, the aggregation state was altered by different quenching techniques. The chemical composition was varied by synthesizing a series of slags. The degree of hydration was studied by developing a thermogravimetric analysis technique and the glass content was determined using microscopy. Minerals were determined using powder x-ray diffraction analysis.

This study is concerned with the metabolism of L-asparagine in Lactobacillus plantarum (ATCC 8014). Theprimary area of investigation is the preliminary characterization of a previously unreported L-asparaginase enzyme in L. plantarum. This L-asparaginase was determined to be an inducible enzyme with variations in its activity level according to the L-asparagine level in the growth medium. L-Glutaminase could not be induced in this organism by L-glutamine, nor would L-glutamine induce the asparaginase activity. These and other studies with amino acid analogs demonstrated the high specificity of both induction and enzymic activity of the asparaginase. Various physical properties of the enzyme were studied. The enzyme was found to be inhibited by adenosine triphosphate (ATP). This inhibition appears to be cooperative in nature and of the type exhibited by allosteric enzymes. These studies should be confirmed on a highly purified enzyme as these preliminary experiments were performed using a crude cell-free extract.

Ligands prepared from various combinations of aldehydes and ketones with the appropriate aminealcohol were complexed with cupric acetate monohydrate. The complexes with O,NO or N,N,O donor atoms were synthesized to study the influences of the ligand on molecular structure, spin-spin interaction, and on the value of the exchange integral. The magnetic data indicated that of the eight Cu(II) complexes discussed, two behaved differently from known analogous compounds. Cu (benzoylacetone :ethanolamine) was compared to Cu(acac:ethanolamine), and Cu(pyrr:oaminophenol) was compared to Cu(acac:o-aminophenol). Each pair of complexes was postulated to have the same molecular structure. The synthesis and characterization of Mn(pyrr:oaminophenol) 2H2 is also discussed. The following physical data were collected and discussed: elemental analysis, melting point, molecular weight, infrared spectra, electronic spectra, and magnetic susceptibility.

Symmetrical cage-annulated podands were synthesized via highly efficient synthetic strategies. Mechanisms to account for the key reaction steps in the syntheses are proposed; the proposed mechanisms receive support from the intermediates that have been isolated and characterized. An unusual complexation-promoted elimination reaction was studied, and a mechanism is proposed to account for the course of this reaction. This unusual elimination may generalized to other rigid systems and thus may extend our understanding of the role played by the host molecules in "cation-capture, anion-activation" via complexation with guest molecules. Thus, host-guest interaction serves not only to activate the anion but also may activate the leaving groups that participate in the complexation. Complexation-promoted elimination provides a convenient method to desymmetrize the cage while avoiding protection/deprotection steps. In addition, it offers a convenient method to prepare a chiral cage spacer by introducing 10 chiral centers into the host system in a single synthetic step. Cage-annulated monocyclic hosts that contain a cage-butylenoxy spacer were synthesized. Comparison of their metal ion complexation behavior as revealed by the results of electrospray ionization mass spectrometry (ESI-MS), alkali metal picrate extraction, and pseudohydroxide extraction with those displayed by the corresponding hosts that contain cage-ethylenoxy or cage-propylenoxy spacers reveals …

A computational chemistry analysis combined with a crystallographic database study of the bonding in late transition metal N-heterocyclic carbene (NHC) complexes is reported. The results illustrate a metal-carbon bond for these complexes, approximately 4% shorter than that of a M-C single bond found in metal alkyl complexes. As a consequence of this result, two hypotheses are investigated. The first hypothesis explores the possibility of multiple-bond character in the metal-carbon linkage of the NHC complex, and the second, considers the change in the hybridization of the carbenoid carbon to incorporate more p character. The latter hypothesis is supported by the results. Analysis of these complexes using the natural bond orbital method evinces NHC ligands possessing trans influence.

In this work, copper bimetallic corrosion and inhibition in ultra large scale interconnect fabrication process is explored. Corrosion behavior of physical vapor deposited (PVD) copper on ruthenium on acidic and alkaline solutions was investigated with and without organic inhibitors. Bimetallic corrosion screening experiments were carried out to determine the corrosion rate. Potentiodynamic polarization experiments yielded information on the galvanic couples and also corrosion rates. XPS and FTIR surface analysis gave important information pertaining inhibition mechanism of organic inhibitors. Interestingly copper in contact with ruthenium in cleaning solution led to increased corrosion rate compared to copper in contact with tantalum. On the other hand when cobalt was in contact with copper, cobalt corroded and copper did not. We ascribe this phenomenon to the difference in the standard reduction potentials of the two metals in contact and in such a case a less noble metal will be corroded. The effects of plasma etch gases such as CF4, CF4+O2, C4F8, CH2F2 and SF6 on copper bimetallic corrosion was investigated too in alkaline solution. It was revealed that the type of etching gas plasma chemistry used in Cu interconnect manufacturing process creates copper surface modification which affects corrosion behavior in alkaline solution. The learning …

Soft-landing ion mobility has applicability in a variety of areas. The ability to produce material and collect a sufficient amount for further analysis and applications is the key goal of this technique. Soft-landing ion mobility has provided a way to deposit material in a controllable fashion, and can be tailored to specific applications. Changing the conditions at which soft-landing ion mobility occurs effects the characteristics of the resulting particles (size, distribution/coverage on the surface). Longer deposition times generated more material on the surface; however, higher pressures increased material loss due to diffusion. Larger particles were landed when using higher pressures, and increased laser energy at ablation. The utilization of this technique for the deposition of silver clusters has provided a solvent free matrix application technique for MALDI-MS. The low kinetic energy of incident ions along with the solvent free nature of soft-landing ion mobility lead to a technique capable of imaging sensitive samples and low mass analysis. The lack of significant interference as seen by traditional organic matrices is avoided with the use of metallic particles, providing a major enhancement in the ability to analyze low mass compounds by MALDI.

When a molecule, which possess a permanent dipole moment is exposed to an intense electric field, its absorption spectrum may be altered. These alterations are manifest as shifts in energy and as changes in band shape and intensity. The electric dichroism of absorption bands can be used to probe the excited state that is formed when a molecule undergoes a transition. The properties that may be investigated include transition polarization, excited state dipole moment and mean polarizability, and field-induced mixing of symmetrically equivalent excited states. The theoretical model and experimental devices that have been developed to determine these properties are presented and discussed. The data, taken in total, and its combination with other existing evidence, adds credence to the assignment of the second excited singlet of aldehydes and ketones to be extravalent, accompanied by relatively large delocalization of electronic charge, and polarized in-planiie and perpendicularly to the C-0 axis.

The temperature dependence of the reactions of halogen atoms Cl and Br with SiH4 and (CH3)3SiH have been investigated with the flash photolysis-resonance fluorescence technique. CCI4 and CH2Br2 were used as precursors to produce Cl and Br atoms, respectively. Experiments gave {k(Cl + SiH4) (295 - 472 K)} = (1.56 +0.11) x 10-1 exp[(2.0 + 0.2) kJ mol'/RT] cm3 s4, {k(Br + SiH4)(295 - 575 K)} = (9.0 + 1.5) x 10-" exp[-(17.0 + 0.6) Id mol'/RT] cm3 s', {k(Cl + (CH3)3SiH)(295 - 468 K)} = (1.24 0.35) x 104 exp[(1.3 + 0.8) Id mol4/RT] cm3 s', and {k(Br + (CH3)3SiH)(295 - 456 K)} = (7.6 + 3.3) x 1010 exp[-(28.4 + 1.3) Id mol'/RT] cm3 s'. The results were compared with values from earlier work.