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Synthesis Of Highly-Strained Gem-Difluoro Compounds By Reaction Of Difluoromethylene With Cycloalkenes, Deyi Yang May 1989

Synthesis Of Highly-Strained Gem-Difluoro Compounds By Reaction Of Difluoromethylene With Cycloalkenes, Deyi Yang

Theses

Trans-Cyclooctene is thought to be more reactive than cis-cyclooctene due to its trans-structure. When cis or trans-clooctene reacts with difluormethylene (:CF2), trans-9,9-difluorobicyclo[ 6,1,0] nonane was generated in much higher yield than cis-9,9-difluorobicyclo[6,1,0]nonane. [PhCF3P+CF2Br]Br- was chosen to be the difluoromethylene precursor in this study. The reason was that the reaction condition for trans-cyclooctene and :CF2 should be at low temperature. Only [PhCF3P+CF2Br]Br- could generate CF2 at lower temperature (e.g. room temperature). We succeeded in the synthesis of trans-9,9-difluorobicyclo[6,1,0]nonane and its cis isomer and …


Relating The Mole Concept And Fundamental Mathematics, Kenneth L. Phillips May 1989

Relating The Mole Concept And Fundamental Mathematics, Kenneth L. Phillips

Abraham S. Fischler College of Education ETD Archive

The high percentage of students with difficulty in solving free-response problems related to the mole concept was addressed by implementation of reading skill strategies and computer aided instruction. Frayer models, semantic mapping and graphic organizers from Reading in the Content Area (RICA) were employed to increase student understanding of the scientific principles involved. Computers and a variety of computer programs from COMPress and Knowledge Factory were used by the target group for review, drill, and practice in relating their math skills to solving problems. The results indicated a considerable increase in the ability to solve problems related to the mole …


Identification Of The Functional Regions Of The Yeast Activator Adr1, Lynne Taylor Bemis Jan 1989

Identification Of The Functional Regions Of The Yeast Activator Adr1, Lynne Taylor Bemis

Doctoral Dissertations

ADR1, a transcriptional activator from the yeast Saccharomyces cerevisiae, is required for activation of the glucose-repressible alcohol dehydrogenase, ADH II (encoded by the ADH2 gene). The ADR1 gene encodes a protein which binds to an upstream activation sequence in the ADH2 promoter. Several methods were used to locate functional regions of the ADR1 protein.

The adr1-1 mutation was identified as a C to G transversion resulting in a nonsense codon at the eleventh codon of ADR1. tRNA-suppressors which substituted an amino acid at the eleventh codon of adr1-1 resulted in a functional adr1-1 protein, indicating that the translational start of …


The Effect Of Reagent Rotation On Gas Phase Reactions, Judith Agnes Harrison Jan 1989

The Effect Of Reagent Rotation On Gas Phase Reactions, Judith Agnes Harrison

Doctoral Dissertations

This dissertation examines the effect of reagent rotation in elementary gas phase reactions. Historically, the effect of rotational excitation of the reagents of a chemical reaction on the reactive cross section has been poorly understood. One of the major reasons for this was the lack of a simple model in which the dynamics could be visualized. In this work, such a model is developed and utilized in order to elucidate trends in reactivity observed upon rotational excitation. Within the context of this model, exact quantum mechanical scattering calculations are performed for a simple atom-diatom system. These exact quantum mechanical probabilities …


Electrochemical And Spectroscopic Characterization Of Bis(Ethylenedithio)Tetrathiafulvalene, Tetramethyltetraselenafulvalene And Their Perchlorate Salts., Roberto Luzon Wong Jan 1989

Electrochemical And Spectroscopic Characterization Of Bis(Ethylenedithio)Tetrathiafulvalene, Tetramethyltetraselenafulvalene And Their Perchlorate Salts., Roberto Luzon Wong

LSU Historical Dissertations and Theses

Electroanalytical methods (cyclic voltammetry (CV), rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) voltammetry) have been used to characterize the oxidation products of bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF or ET) and tetramethyltetraselenafulvalene (TMTSF) in two commonly used solvents, acetonitrile (CH$\sb3$CN) and 1,1,2-trichloroethane (1,1,2-TCE). Cyclic voltammetry has revealed that the electro-oxidations of ET and TMTSF each occur initially via two one-electron steps representing the formation of the monocation radical and dication species. The electrochemical behaviors of TMTSF and ET in both solvents are summarized. UV/VIS spectroscopy was used to characterize TMTSF, ET and their perchlorate salts in solution. Solution spectra of TMTSF, …


Mechanism Of Toxicity Of 2-Thiotriazone (Ttz) In Rats., Twintillia Murphy Tate Jan 1989

Mechanism Of Toxicity Of 2-Thiotriazone (Ttz) In Rats., Twintillia Murphy Tate

LSU Historical Dissertations and Theses

The mechanism of action of 2-thiotriazone (TTZ) was evaluated in adult and immature rats of both sexes. TTZ produced marked pulmonary toxicity in rats that was both age and sex-dependent. It was highly toxic in male rats (oral LD50 of 4.6 mg/kg and ip LD50 of 1.4 mg/kg). Female rats were more resistant than males and immature rats (30-40 days of age) were totally resistant to TTZ toxicity. Gross and histological examination of lung tissue from rats exposed to TTZ showed severe pulmonary edema, effusion and mottling of the lungs. Significant increases in lung weights were also observed. Diethylmaleate (DEM) …


The Synthesis Of Constrained And Benzannulated Derivatives Of The Essential Amino Acids Tyrosine And Tryptophan., Marco A. Vela Jan 1989

The Synthesis Of Constrained And Benzannulated Derivatives Of The Essential Amino Acids Tyrosine And Tryptophan., Marco A. Vela

LSU Historical Dissertations and Theses

Benzannulated and a series of constrained derivatives of the essential amino acids tyrosine and tryptophan were synthesized. The synthesis of the two benzannulated tyrosine analogs followed traditional synthetic protocols that basically consisted of obtaining key oxazolones and further elaboration to the target amino acids; the latter compounds were obtained as racemic mixtures. All the reaction intermediates were fully characterized spectroscopically, and when possible, structure proof was established by X-ray crystallographic determinations. Asymmetric hydrogenation studies on the intermediate (Z)-2-benzoylaminoacrylic acids were undertaken in an effort to obtain enantiomerically pure materials. The products were, in fact, chiral upon hydrogenation in the presence …


Interpretation Of Solid State Deuterium Nmr Spectroscopic Parameters., Kermin Guo Jan 1989

Interpretation Of Solid State Deuterium Nmr Spectroscopic Parameters., Kermin Guo

LSU Historical Dissertations and Theses

Solid-state deuterium NMR spectroscopic parameters including the deuterium quadrupole coupling constant and asymmetry parameter are interpreted in both theoretical and experimental aspects. Ab initio molecular orbital calculations were performed on the alkali metal hydrides, toluene, thymine, acetic acid dimer, and phenylacetic acid molecules with different conformations. In the alkali metal hydrides, the electric field gradient at the hydrogen atom site was calculated in three model systems: terminal metal hydride, bridging metal hydride, and dihydrogen adducts. The effect of metal hydride geometry on the deuterium quadrupole coupling constant was examined. The results can be used in the assignment and interpretation of …


Development Of A Karplus-Type Relationship For Solid State Deuterium Nuclear Magnetic Resonance Spectroscopy., Margaret Alice Callaghan Jackisch Jan 1989

Development Of A Karplus-Type Relationship For Solid State Deuterium Nuclear Magnetic Resonance Spectroscopy., Margaret Alice Callaghan Jackisch

LSU Historical Dissertations and Theses

This dissertation is the first application of a Karplus-type relationship to solid-state deuterium NMR spectroscopy. In particular zero-field high-resolution deuterium adiabatic demagnetization in the laboratory frame (ADLF) spectroscopy has been used to distinguish between two inequivalent deuterium positions in alpha substituted arylacetic acids. High resolution spectra with linewidths of 1-2 kHz were observed and have been used successfully to document the inequivalent positions both by single and double transition spectra. Further, small applied fields, inducing Zeeman splitting, have proven the deuterons observed to be from the transition frequencies of two different deuterons. Individual spectra are shown for all compounds included …


Characterization And Potential Applications Of Cascade Arborols And Preparation Of Metallocyclic Palladium(Ii) And Rhodium(Iii) Complexes., Gregory Rufus Baker Jan 1989

Characterization And Potential Applications Of Cascade Arborols And Preparation Of Metallocyclic Palladium(Ii) And Rhodium(Iii) Complexes., Gregory Rufus Baker

LSU Historical Dissertations and Theses

A new class of specifically shaped, highly branched molecules was prepared where the branches emanate from tetrahedral carbons. This class of molecules has been named arborols because of their topological similarity to the "Leeuwenberg" model for tropical trees. The arborols were synthesized a layer (or tier) at a time to generate cascade spheres, where the number of terminal groups per sphere increases exponentially. Initially, molecules possessing a single cascade sphere attached to simple hydrocarbon chains were prepared to develop synthetic methods and provide proof-of-concept. Several series of dumbbell shaped, two-directional arborols were prepared, where two cascade spheres are connected via …


The Structural And Functional Roles Of Critical Amino Acid Residues In Drosophila Alcohol Dehydrogenase., Zhuo Chen Jan 1989

The Structural And Functional Roles Of Critical Amino Acid Residues In Drosophila Alcohol Dehydrogenase., Zhuo Chen

LSU Historical Dissertations and Theses

Alcohol dehydrogenase (ADH, alcohol:NAD oxidoreductase, EC1.1.1.1) from Drosophila melanogaster (DmADH) is unique among alcohol dehydrogenases in metal ion requirement, substrate preference, and stereospecificity of hydride transfer. In order to study this unique enzyme, the first part of this dissertation reports the construction and expression of DmADH cDNA in E. coli hosts. The second part of the dissertation shows the structural function of glycine-14 in putative NAD-binding domain of DmADH. The comparison of DmADH to horse liver ADH suggests that glycine-14 in DmADH is located at the first position of a "conserved sequence" which maintains the tight turn structure positioned in …


Remote In-Situ Detection Of 2,4,6-Trinitrotoluene And Other Explosives Using Fiber Optics, Yunke Zhang Jan 1989

Remote In-Situ Detection Of 2,4,6-Trinitrotoluene And Other Explosives Using Fiber Optics, Yunke Zhang

Doctoral Dissertations

The goal of this research was to develop methods for the in-situ determination of 2,4,6-trinitrotoluene (TNT) and other polynitroaromatic compounds in groundwater. The first approach was to use an adsorbent to preconcentrate TNT for direct determination. Poly(vinyl alcohol) was crosslinked with glutaraldehyde to form a clear gel that is transparent into the ultraviolet. The volume and swelling of the gel can be controlled by varying the amount of glutaraldehyde. The coefficient for TNT partitioning between the gel and water is 1.4. The gel offers important advantages as a matrix for chemical sensor development, but is not suitable for determining TNT …


Synthesis And Reactions Of Phosphonito Polymetallic Complexes And Halogen Oxidation Of Cyclo-Tetraphosphoxane Molybdenum Cage Complexes, Carmen Valdez Jan 1989

Synthesis And Reactions Of Phosphonito Polymetallic Complexes And Halogen Oxidation Of Cyclo-Tetraphosphoxane Molybdenum Cage Complexes, Carmen Valdez

Doctoral Dissertations

Mixed-valent tetrametallic complexes of the type Mo$\sb2\lbrack$M(CO)$\sb4$(PhPO$\sb2$)$\sb2\rbrack\sb2\sp{4-}$ (M = Cr, Mo, W) were synthesized by the nucleophilic attack of the phosphonito metallo-ligand cis-M(CO)$\sb4$(PhPO$\sb2$)$\sb2\sp{4-}$ on dimolybdenum tetraacetate. These complexes were characterized by elemental analyses and NMR, IR, and UV-Vis spectroscopy. The x-ray crystal structure for the tetra-molybdenum complex indicates a M-M bondlength of 2.186(2). Only weak interactions were found with potential axial ligands such as amines, phosphines and isonitriles. Oxidation with four equivalents of iodine occurred at the Mo(O) sites yielding Mo$\sb2\lbrack$Mo(CO)$\sb3$I$\sb2$(PhPO$\sb2$)$\sb2\rbrack\sb2\sp{4-}$ with new seven-coordinate Mo(II) sites. The phosphorus-31 NMR spectrum of this complex exhibits temperature-dependent behavior indicating rapid geometric isomerization …


Characterization Of Cell Cycle Changes In Polyamine-Depleted Hela Cells, Robert Anthony Koza Jan 1989

Characterization Of Cell Cycle Changes In Polyamine-Depleted Hela Cells, Robert Anthony Koza

Doctoral Dissertations

HeLa cells were synchronized for S-phase DNA synthesis and simultaneously depleted of polyamines by the addition of the inhibitor of polyamine biosynthesis, $\alpha$-difluoromethylornithine (DFMO).

DFMO reacts catalytically with and irreversibly inhibits the enzyme ornithine decarboxylase (ODC) thereby preventing the biosynthesis of the polyamines putrescine, spermidine, and spermine.

The depletion of polyamines in HeLa cells inhibits cellular processes such as DNA synthesis and proliferation. These processes could be reversed by the addition of spermidine 10-12 hours before S-phase DNA synthesis was initiated.

Nuclear reconstitution procedures were utilized to determine the location of the deficiency in polyamine-depleted cell nuclei. It was shown …


Ring-Chain Tautomerism Studies In 2-(2-Hydroxyethoxy)-Benzaldehydes And 2-(5-Hydroxy-3-Oxa-Pentyloxy)-Benzaldehydes, Adam John Jaglowski Jan 1989

Ring-Chain Tautomerism Studies In 2-(2-Hydroxyethoxy)-Benzaldehydes And 2-(5-Hydroxy-3-Oxa-Pentyloxy)-Benzaldehydes, Adam John Jaglowski

Doctoral Dissertations

The synthesis, characterization and ring-chain tautomerism studies of substituted 2-(2-hydroxyethoxy)-benzaldehydes and 2-(5-hydroxy-3-oxa-pentyloxy)-benzaldehydes are described. The benzaldehydes, substituted in the 3-, 5- or 3,5-positions with either nitro, bromo, chloro, iodo, phenyl or methyl groups, were studied by proton and carbon-13 Nuclear Magnetic Resonance spectroscopy as a means of determining their potential to exist as ring-chain tautomeric mixtures. The 2-(5-hydroxy-3-oxa-pentyloxy)-benzaldehydes and 5-substituted 2-(2-hydroxyethoxy)-benzaldehydes exist solely as the chain tautomers in solution, while 3- and 3,5-substituted 2-(2-hydroxyethoxy)-benzaldehydes are mixtures of ring and chain tautomers in solution. A correlation of K with substituents indicates that the size of the aromatic substituent in the 3-position …


Development Of A Glucose Sensor Based On Competitive Binding And Laser-Excited Fluorescence, Richard William Bauer Jan 1989

Development Of A Glucose Sensor Based On Competitive Binding And Laser-Excited Fluorescence, Richard William Bauer

Doctoral Dissertations

An optical glucose sensor has been developed using competitive binding in conjunction with energy transfer. Sensor response is based on competition between glucose and dextran for a limited number of binding sites on the protein concanavalin A (conA). The system is optically monitored using fluorescent donor-acceptor dye pairs labeled to concanavalin A and dextran. When the dyes are sufficiently close, on the order of 50 A, energy is transferred from the donor emission band to the overlapping excitation band of the acceptor. This nonradiative, singlet-singlet transfer of energy enhances the acceptor emission at the expense of donor emission.

In absence …


Solvatochromic Indicators For Fiber Optic Chemical Sensors, Ziad Munib Shakhsher Jan 1989

Solvatochromic Indicators For Fiber Optic Chemical Sensors, Ziad Munib Shakhsher

Doctoral Dissertations

The goal of this thesis was to develop and evaluate solvatochromic indicators for fiber optic chemical sensors. Interaction with analyte modifies the polarity of the immobilized indicator environment leading to a shift in their fluorescence spectra. Three systems were studied.

In the first study a cationic fluorescent probe, 5-dimethylaminonaphthalene-1-sulfonamidoethyltrimethylammonium ion (DA$\sp+$), was equilibrated with unmodified- and hydrocarbon bonded-silicas. In solution and unmodified silica, maximum DA$\sp+$ fluorescence shifts to longer wavelengths with increasing percentages of methanol, tetrahydrofuran and acetonitrile in water. On hydrocarbon bonded silicas, however, DA$\sp+$ emission maxima in water occur at shorter wavelengths indicating a very nonpolar environment. This …


Development Of An Analytical Method For The Determination Of Extractable Nitroaromatics And Nitramines In Soils, Thomas F. Jenkins Jan 1989

Development Of An Analytical Method For The Determination Of Extractable Nitroaromatics And Nitramines In Soils, Thomas F. Jenkins

Doctoral Dissertations

An analytical method was developed to determine the concentrations of HMX, RDX, TNB, DNB, tetryl, TNT and 2,4-DNT in soil. The method relies on solvent extraction with analysis by reversed-phase liquid chromatography.

The extraction step was studied in terms of process kinetics and recovery. Two solvents (acetonitrile and methanol) and four extraction techniques (Soxhlet, ultrasonic bath, mechanical shaker and homogenizer-sonicator) were compared. Ultrasonic bath extraction with acetonitrile was selected based on extraction kinetics, overall analyte recovery, sample throughput, and instability of analytes at elevated temperature. The rate of extraction of analytes from field-contaminated soil was shown to be much slower …


The Synthesis And Characterization Of Transition Metal Complexes Of Triazacyclododecane And Its Tri-N-Methyl And Orthoamide Derivatives, Steven Paul Vankouwenberg Jan 1989

The Synthesis And Characterization Of Transition Metal Complexes Of Triazacyclododecane And Its Tri-N-Methyl And Orthoamide Derivatives, Steven Paul Vankouwenberg

Doctoral Dissertations

The comparative study of the mono- and tricyclic triamine complexes based on twelve-membered rings and the group 6 and group 10 metals has been initiated. The four ligands used in this study were 1,5,9-triazacyclododecane ( (12) aneN$\sb3$), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me$\sb3$ (12) aneN$\sb3$), 1,5,9-triazacyclododecane orthoformamide (orthoformamide) and 1,5,9-triazacyclododecane orthoacetamide (orthoacetamide). Complexes with zero-valent group 6 metal (Cr, Mo, W) tricarbonyls were characterized and the single-crystal X-ray structures determined for each ligand-molybdenum tricarbonyl complex. Complexes with nickel(II), palladium(II) and platinum(IV) have been characterized and the single-crystal X-ray structure of orthoacetamide PdCl$\sb2$ has been determined. The tricyclic orthoamides have been found to be less …


Deoxyribonucleases Expressed In Competence-Induced Com And Spo0 Mutants Of Bacillus Subtilis, Billy Robert Mcgrew Jan 1989

Deoxyribonucleases Expressed In Competence-Induced Com And Spo0 Mutants Of Bacillus Subtilis, Billy Robert Mcgrew

Doctoral Dissertations

The inclusion of 1% casein in buffer used to reactivate enzymes subjected to SDS-polyacrylamide electrophoresis resulted in faster and more complete restoration of nuclease and B-galactosidase enzyme activities. Enzyme activities which were absent from gels during longer wash procedures were detectable with this technique. The threshold of detection of two-dimensionally separated Deoxyribonuclease I was 1 picogram, tenfold lower than for previously reported wash procedures. Addition of BSA at concentrations above 50 ug/ml to nuclease gels was found to result in less effective detergent removal during wash procedures and reduced recovery of enzyme activity.

General and specific nuclease expression patterns were …


The Metabolism Of 4-Deoxy-4-Fluoro-D-Glucose In Pseudomonas Putida., Diego Delfino Livio. Sbrissa Jan 1989

The Metabolism Of 4-Deoxy-4-Fluoro-D-Glucose In Pseudomonas Putida., Diego Delfino Livio. Sbrissa

Electronic Theses and Dissertations

Uniformly carbon-14-labelled 4-deoxy-4-fluoro-D-glucose (D-(U-$\sp{14}$C) 4FG) is synthesized for the first time and used to follow the fate of 4-deoxy-4-fluoro-D-glucose (4FG) in Pseudomonas putida. Following a 24-hour incubation of a suspension of glucose-grown whole cells of P. putida with 1 millimolar(mM) D- (U-$\sp{14}$C) 4FG under conditions giving a 95% release of F$\sp-$, less than 1% of the radiolabel is found to be covalently associated with the peptidoglycan present in the cell-envelope fraction, more than 50% of the radiolabel accumulates in the suspending medium, and as much as 5% of the radiolabel is recovered as a volatile product which appears to be …


Phosphorus Sorption Characteristics Of Acid Sulfate Soils Of Thailand., Asdaporn Krairapanond Jan 1989

Phosphorus Sorption Characteristics Of Acid Sulfate Soils Of Thailand., Asdaporn Krairapanond

LSU Historical Dissertations and Theses

The study of P-sorption by soils has practical interest but little is known on the P-sorption characteristics of acid sulfate soils of Thailand, particularly under reduced soil conditions. The effects of pH, redox potential, and various forms of Fe, Al, and Mn on P-sorption of the actual acid sulfate soils (Sulfic Tropaquept) and the para-acid sulfate soil (Typic Tropaquept) were studied in laboratory microcosms. Soil suspensions with a soil to 0.01 M CaCl$\sb2$ solution ratio of 1:7 were incubated under various pH and redox potential conditions. After the incubation period, the soil suspensions were equilibrated with KH$\sb2$PO$\sb4$ ranging from 0 …


Chapter I. The Synthesis, Conformational Analysis And Catalytic Properties Of Four Chiral (Non-Racemic) 4-Substituted Quinolizidines. Chapter Ii. Alkylation Reactions Of Derivatives Of The Camphor-Imine Of T-Butyl-Glycine., Luca Carmine. Matassa Jan 1989

Chapter I. The Synthesis, Conformational Analysis And Catalytic Properties Of Four Chiral (Non-Racemic) 4-Substituted Quinolizidines. Chapter Ii. Alkylation Reactions Of Derivatives Of The Camphor-Imine Of T-Butyl-Glycine., Luca Carmine. Matassa

Electronic Theses and Dissertations

Chapter I. The synthesis of 4R, 10R, 11R, and 4S, 10R, 11S 4- (1-hydroxy-2-(benzyloxy)ethyl) quinolizidine (76a and 76b); and 4-(1,2-dihydroxyethyl)quinolizidine (78a and 78b) in enantiomerically pure form has been achieved. The chiral centers were established by formation of a chiral 2-substituted piperidine and cyclization of optically active epoxides. The solution conformation of these molecules (shown below) have been determined by 300 MHz proton NMR measurements. Amino alcohols 76a and 78a were found to exist in a trans-fused 6,6 ring junction whereas 76b and 78b were found to exist in a cis-fused 6,6 ring junction. The metal salts of diastereomeric quinolizidines …


Diffusion Independent, Bimolecular, Photoinduced Electron Transfer Reactions, Joyce Elizabeth Stilborn Jan 1989

Diffusion Independent, Bimolecular, Photoinduced Electron Transfer Reactions, Joyce Elizabeth Stilborn

Digitized Theses

A variety of expressions have been developed which relate the Gibbs energy of activation to the net Gibbs energy change of a reaction. One of these, the Marcus relation, was developed specifically for outersphere electron transfer reactions. It predicted that, as the reaction exergonicity increased, the activation energy would decrease to zero and then increase. Consequently, the reaction rate constant should increase to a maximum and then decrease in the so-called inverted region.;Extensive investigation over many years failed to find evidence for the inverted region. Recently, five types of experiments have yielded clear evidence of inverted behavior. In all five …


Receptor Arrangement In Myoblasts And Model Membranes, Ingrid Evelyn Mehlhorn Jan 1989

Receptor Arrangement In Myoblasts And Model Membranes, Ingrid Evelyn Mehlhorn

Digitized Theses

Glycosphingolipids are the carbohydrate-bearing lipids of animal cell surfaces. They are being investigated for their structural effects, for their role as recognition sites for hormones, toxins, viruses, and for their involvement in cell-cell interactions. Their physical behaviour in membranes--i.e., their exposure, distribution, peculiar acyl chain characteristics, sugar headgroup arrangement, and interactions--have become questions of considerable debate since these are the very factors thought to regulate their roles as structural components and attachment/recognition sites.;A major interest for us has been to apply freeze-etch electron microscopy to receptor studies in membranes. We developed its use for glycoproteins in cultured cell membranes and …


Studies In Asymmetric Catalysis, Fan-Chou Xu Jan 1989

Studies In Asymmetric Catalysis, Fan-Chou Xu

Digitized Theses

The homogeneous, asymmetric hydrosilylation of prochiral ketones using chiral Rh catalysts of the amphos, P-N, and diamphos, P-N-N, chelate ligands was studied in both solution and the solid state using X-ray crystallographic and spectroscopic techniques, including {dollar}\sp1{dollar}H and {dollar}\sp{lcub}31{rcub}{dollar}P NMR, Visible, Infra Red, and Mass Spectroscopy. These studies provided a basis for relating the catalyst shape to the optical yield, and allowed the elucidation of a mechanistic scheme for homogeneous asymmetric hydrosilylation. In a certain favourable case, an oxidative addition produce RhHCl(SiCl{dollar}\sb3{dollar})(PPh{dollar}\sb3)\sb2{dollar} was isolated and characterized by a single crystal X-ray diffraction study.;In tests for the hydrosilylation of prochiral ketones …


Coordination Chemistry Of A Coordinatively Unsaturated Trinuclear Platinum Cluster, Arleen Marie Bradford Jan 1989

Coordination Chemistry Of A Coordinatively Unsaturated Trinuclear Platinum Cluster, Arleen Marie Bradford

Digitized Theses

This thesis examines the reactivity of the coordinatively unsaturated triplatinum cluster (Pt{dollar}\sb3(\mu\sb3{dollar}-CO){dollar}(\mu{dollar}-dppm){dollar}\sb3\rbrack{dollar} (PF{dollar}\sb6\rbrack \sb2{dollar}, 1. The complex can act as a model for a triangle of platinum atoms on a Pt(111) surface and this thesis describes studies of its reactivity towards various main group reagents.;The halide ions, Cl{dollar}\sp-{dollar}, Br{dollar}\sp-{dollar} and I{dollar}\sp-{dollar}, yielded the clusters (Pt{dollar}\rm\sb3(\mu\sb3{dollar}-CO){dollar}(\mu\sb3{dollar}-X)({dollar}\mu{dollar}-dppm){dollar}\sb3\rbrack \sp{lcub}1+{rcub}{dollar} which were characterized spectroscopically. Attempts were made to investigate the bonding in these systems with respect to the degree of ionic, or covalent, character in the Pt{dollar}\rm\sb3(\mu\sb3{dollar}-X) bonds through ligand exchange studies.;Monodentate tertiary phosphines and phosphites yielded the clusters (Pt{dollar}\rm\sb3(\mu{dollar}-CO)L{dollar}(\mu{dollar}-dppm){dollar}\sb3\rbrack\sp{lcub}2+{rcub}{dollar}, L = phosphine or …


The Coordination Chemistry Of Hexafluoroacetone Hydrate, Rosemary Catherine Hynes Jan 1989

The Coordination Chemistry Of Hexafluoroacetone Hydrate, Rosemary Catherine Hynes

Digitized Theses

This thesis discusses the coordination chemistry of the fluorinated gem-diol, (CF{dollar}\sb3)\sb2{dollar}C(OH){dollar}\sb2{dollar}, "hexafluoroacetone hydrate" (HFAH). Due to the electron-withdrawing ability of the CF{dollar}\sb3{dollar} groups, the protons of this diol are acidic. Reactions of the diol with metal chlorides and alkali metal hydroxides were found to give fluorinated alkoxide complexes in which HFAH adopted four distinct coordination modes. The nature of the metal, and the amount and steric requirements of the coligand, if any, used, were identified as major factors in determining which coordination mode was adopted. The four observed modes are (i) as a chelating dialkoxide, {dollar}\rm\sp-OC(CF\sb3)\sb2O\sp-{dollar}, (ii) as a dimerized, …


Purification And Characterization Of Four Novel Proteases From The Periplasmic Space Of Escherichia Coli K12, Indrasen Sivalingam Vaithilingam Jan 1989

Purification And Characterization Of Four Novel Proteases From The Periplasmic Space Of Escherichia Coli K12, Indrasen Sivalingam Vaithilingam

Digitized Theses

Intracellular proteases are ubiquitous in nature. This extensive distribution necessarily implicates their participation in a wide variety of cellular events. Escherichia coli, contains a variety of proteases and peptidases. For the most part, the known endoproteases of E. coli have been characterized from cells grown to stationary phase on enriched media. Surprisingly, no studies have addressed the question of what proteases are present in exponentially growing E. coli, despite the fact that significant protein turnover occurs.;Previous studies from this laboratory revealed the presence of a unique Ca{dollar}\sp{lcub}2+{rcub}{dollar}-activated proteolytic activity in E. coli. This activity was maximal in mid-log grown cells …


Regulation Of Cyclic-Amp-Dependent Protein Kinases During Skeletal Myogenesis, Ian Anthony Lorimer Jan 1989

Regulation Of Cyclic-Amp-Dependent Protein Kinases During Skeletal Myogenesis, Ian Anthony Lorimer

Digitized Theses

L6 myoblasts are a permanent rat skeletal myoblast cell line which differentiates in culture to form multinucleate myotubes. The regulation of the levels of cAMP-dependent protein kinases during myogenesis in L6 was studied, as these enzymes have been proposed to be involved in the control of this process. Measurement of the mRNA levels for the type I regulatory subunit (R{dollar}\sb{lcub}\rm I{rcub}{dollar}) of cAMP-dependent protein kinase, and studies on the rates of transcription from the gene coding for this protein, showed that the increase in R{dollar}\sb{lcub}\rm I{rcub}{dollar} which occurs during myogenesis is is not regulated transcriptionally. Measurement of R{dollar}\sb{lcub}\rm I{rcub}{dollar} half-lives …