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Digitized Theses

1986

Chemistry

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The Magnesium(2+)-Dependent Phosphatidate Phosphohydrolase Of Rat Lung, Paul Albert Walton Jan 1986

The Magnesium(2+)-Dependent Phosphatidate Phosphohydrolase Of Rat Lung, Paul Albert Walton

Digitized Theses

The Mg('2+)-dependent phosphatidate phosphohydrolase (PAPase) activity has been studied in rat lung subcellular fractions, and a malignant cell line (A549) which serves as a model of human Type II pneumocytes. Properties of this activity, which used a chemically-defined substrate of equimolar PC and PA, were equivalent to those found using membrane-bound substrate. Microsomes washed in buffers containing high salt concentrations displayed a decrease in the PAPase which could be quantitatively recovered in the wash supernatant. Mg('2+)-independent activity remained associated with the microsomes under these conditions. These microsomes displayed a reduced capacity to label glycerolipids from ('14)C -glycerol phosphate. Labelling could …


Work Towards The Total Synthesis Of Patchouli Alcohol And Approaches To Cycloseychellene, Murray Douglas Bailey Jan 1986

Work Towards The Total Synthesis Of Patchouli Alcohol And Approaches To Cycloseychellene, Murray Douglas Bailey

Digitized Theses

The synthesis of polycyclic compounds usually requires numerous synthetic operations in order to construct the desired carbon skeletons. A simple procedure termed a bicycloannulation allows for the generation of one of these ring systems in one synthetic operation. The tricyclo 3.2.1.0('2,7) octane ring system incorporates a two carbon bridge cross a cyclohexane ring which includes at one end a cyclopropane ring. This tricyclic carbon skeleton is a highlighting feature of a number of terpenoids, including the sesquiterpene cycloseychellene. Beginning with a substituted cyclohexenone, the bicycloannulation allows for the construction of all but one of the rings in this tetracyclic sesquiterpene. …


An Investigation Of Dinuclear Alkylidene-Bridged Carbonyl Complexes, William John Laws Jan 1986

An Investigation Of Dinuclear Alkylidene-Bridged Carbonyl Complexes, William John Laws

Digitized Theses

The objective of this research was to synthesize binuclear (mu)-alkylidene complexes of manganese or cobalt, to study their chemical properties, and to assess their potential as model intermediates in the Fischer-Tropsch synthesis.;Excess diazoalkane addition to Mn(,2)(CO)(,4)((mu)-CO)((mu)-dppm)(,2) ; dppm = Ph(,2)PCH(,2)PPh(,2), produces 1:1 adducts of formula Mn(,2)(CO)(,4) (mu)-C(O)CHRN(,2) ((mu)-dppm)(,2) (R = H,Me,CO(,2)Et) containing a novel metallacycle derived from coupling of the diazoalkane molecule with a carbonyl ligand. The structure was established by an X-ray analysis of Mn(,2)(CO)(,4) (mu)-C(O)CH(,2)N(,2) ((mu)-dppm)(,2) . Photolysis or thermolysis of each adduct regenerates Mn(,2)(CO)(,4)((mu)-CO)((mu)-dppm)(,2) .;A series of ((mu)-alkylidene)dicobalt complexes was prepared via CO displacement from Co(,2)(CO)(,4)((mu)-CO)(,2)((mu)-dppm) at …


Trinuclear Clusters Of Palladium And Platinum, Brian Richard Lloyd Jan 1986

Trinuclear Clusters Of Palladium And Platinum, Brian Richard Lloyd

Digitized Theses

The syntheses of trinuclear clusters, M(,3)((mu)(,3)-CO)((mu)-dppm)(,3) ('2+); M = Pt or Pd; dppm = Ph(,2)PCH(,2)PPh(,2), has been accomplished with the structural features of both the platinum and palladium clusters having been investigated by spectroscopic and x-ray crystallographic structure determinations. The mechanism of formation has been shown to involve the reduction of M(II) monomers through M(I)(,2) dimers to M(2/3)(,3) trimers with parallel oxidation of CO(,(g)) to CO(,2(g)), in aqueous media.;The selective attachment of halide ions to the triply bridging site of Pd(,3)((mu)(,3)-CO)((mu)-dppm)(,3) ('2+) has been established and the equilibrium constants for coordination have been shown to follow the sequence of I('-) …


Studies In Asymmetric Hydrosilation, Ian Douglas Mckay Jan 1986

Studies In Asymmetric Hydrosilation, Ian Douglas Mckay

Digitized Theses

The ligand amphos forms square planar Rh(I) complexes which catalyze the asymmetric homogeneous hydrosilation of ketones in up to 72% optical yield. Initially, modifications of the aminophosphine ligand, N,N-dimethyl-1-(o-(diphenylphosphino)phenyl)ethylamine, amphos, were prepared and their Rh complexes were tested as catalysts for the asymmetric hydrosilation of ketones. In the second approach x-ray crystallography, spectroscopic techniques, and conformational energy calculations were used to investigate the relationship between catalyst shape and efficiency.;Three modifications of the amphos ligand were prepared. In the first two the phenyl substituents on P were replaced by either cyclohexyl groups, dicyphos, or tert-butyl groups dibutphos. In the third modification …


Atomic And Molecular Photoelectron Spectroscopy Studies Using Synchrotron Radiation, Brian Wayne Yates Jan 1986

Atomic And Molecular Photoelectron Spectroscopy Studies Using Synchrotron Radiation, Brian Wayne Yates

Digitized Theses

Using photons from the Canadian Synchrotron Radiation Facility (CSRF) at the Tantalus electron storage ring, gas phase photoelectron spectra of the Xe 4d(,3/2,5/2) core level, and the valence orbitals of CF(,4), SiF(,4), CF(,3)I, and XeF(,2) have been obtained as a function of photon energy. Theoretical branching ratios and partial cross sections obtained from MS-X(alpha) calculations, are compared with experiment for the molecular cases. These atomic and molecular systems were studied in order to further our understanding of shape resonances and many-body effects in photoionization.;The Xe 4d(,5/2):4d(,3/2) spin-orbit branching ratio has been accurately determined from 74 to 150 eV photon energy. …


Structure And Function Of The Src Gene Of Rous Sarcoma Virus And The Human Cellular Src Gene, Stephen Kent Anderson Jan 1986

Structure And Function Of The Src Gene Of Rous Sarcoma Virus And The Human Cellular Src Gene, Stephen Kent Anderson

Digitized Theses

The Rous sarcoma virus (RSV) src gene (v-src) is one of that most extensively studied oncogenes, yet the mechanism by which it transforms virus-infected cells remains unsolved. The study of mutants of RSV provides considerable information on the function of the v-src protein (p60('v-src)).;Characterization of the chicken cellular counterpart of the v-src gene (c-src) has provided clues as to the alterations required to produce an oncogene from a normal cellular gene (proto-oncogene). Characterization of the human c-src gene will be useful for future studies aimed at detecting possible human c-src alterations associated with human neoplastic disorders.;The nucleotide sequence of the …


Biochemical Studies Related To The Progression Of Muscular Dystrophy In The Um-X71 Syrian Hamster, Henry Joseph Klamut Jan 1986

Biochemical Studies Related To The Progression Of Muscular Dystrophy In The Um-X71 Syrian Hamster, Henry Joseph Klamut

Digitized Theses

In order to establish a basis for studies of the development of the polymyopathy of the UM-X7.1 hamster strain, primary tongue myoblast and skin fibroblast cultures were prepared and characterized in terms of established criteria for growth and differentiation. Clonal analysis of myoblast cultures indicated that 80% of colonies judged to be fusion-competent had differentiated. Dystrophic myoblasts displayed a significantly higher plating efficiency, a longer doubling time, and a lower day-7 creatine kinase activity as compared to normal, whereas dystrophic fibroblasts exhibited significant decreases in day-2 creatine kinase and day-7 myokinase activities.;An assessment of ornithine (ODC) and S-adenosylmethionine (SAMDC) decarboxylase …


Studies On A Fluorinated Alkoxy-Phosphino Ligand, Craig Duvall Montgomery Jan 1986

Studies On A Fluorinated Alkoxy-Phosphino Ligand, Craig Duvall Montgomery

Digitized Theses

The synthesis and coordination chemistry of a fluorinated alkoxy-phosphino hybrid ligand is described. The fluorinated alcohol PH(,2)PCH(,2)C(CH(,3))(,2)OH,HL('1), is readily deprotonated in solution giving a bidentate, uninegative ligand, L('1) , containing both hard and soft donors, the alkoxide and phosphine respectively. Alternately the ligand in its protonated form, HL('1), can serve as monodentate phosphine ligand. The ligand coordinates, as a chelate, to both hard (Rh('3+), Co('2+), Ni('2+)) and soft (Cu('+), Pt('2+), Pd('2+), Pt('4+)) metals. In the case of platinum, a variety of complexes were prepared: cis- and trans- Pt(HL('1))(,2)Cl(,2) , Pt(L('1))(,2) , cis- and trans- Pt(HL('1))(L('1))Cl , Pt(PR(,3))(L('1))Cl (where PR(,3) = …


The Cytoplasmic Membrane Carbon(4)-Transport Components In Escherichia Coli K12: Identification And Purification Studies, Katherine Elizabeth Walker Jan 1986

The Cytoplasmic Membrane Carbon(4)-Transport Components In Escherichia Coli K12: Identification And Purification Studies, Katherine Elizabeth Walker

Digitized Theses

The C(,4)-dicarboxylate transport system of Escherichia coli K12 is responsible for the active uptake of succinate, fumarate and malate. Genetic and biochemical evidence has indicated that at least three distinct components appear to be involved in this transport process. Two of these transport components are the cytoplasmic membrane-bound succinate binding proteins, SBP1 and SBP2, which are coded for by the dctB (16 minutes) and dctA (78 minutes) genes respectively. Early work on these two transport proteins involved their isolation via aspartate-Sepharose chromatography from detergent-solubilized cytoplasmic membrane vesicles. The impurity of the isolated dicarboxylate transport proteins necessitated the development of techniques …