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Electronic Theses and Dissertations

1994

Chemistry

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The Syntheses And Structures Of Organoaluminum Amides And Imides With Polydentate Amines., Steven James. Trepanier Jan 1994

The Syntheses And Structures Of Organoaluminum Amides And Imides With Polydentate Amines., Steven James. Trepanier

Electronic Theses and Dissertations

This thesis deals with the syntheses and structures of organoaluminum amides and imides using polydentate amines. Various bidentate and tridentate amines were reacted with trimethylaluminum to yield complexes with uncommon structural features. The reaction between trimethylaluminum and N-phenylethylenediamine produces a monomeric dialkylaluminumamido complex and a trimeric monoalkylaluminumamido complex. The structures of $\rm Me\sb2Al(NH\sb2,CH\sb2CH\sb2NPh),$ 2.1, and $\rm (MeAl(NHCH\sb2CH\sb2NPh))\sb3,$ 2.2 are presented. The reaction between trimethylaluminum and 8-aminoquinoline in a 1:2 ratio affords a monomeric monoalkylaluminumamido complex, while in a 2:1 ratio a tetranuclear imido complex is formed. Reaction of this tetranuclear complex with one equivalent of molecular oxygen converts a methyl …


Thiacyclophane Complexes Of Silver(I), Rhodium(I), Iridium(I) And Ruthenium(Ii)., Hilary Anne. Jenkins Jan 1994

Thiacyclophane Complexes Of Silver(I), Rhodium(I), Iridium(I) And Ruthenium(Ii)., Hilary Anne. Jenkins

Electronic Theses and Dissertations

This thesis deals with the synthesis and characterization of several Ag(I), Rh(I), Ir(I), and Ru(II) complexes of tridentate crown thioether ligands. The incorporation of a rigid xylyl group into the macrocyclic backbone causes the ligand 2,5,8-trithia- (9) -o-cyclophane, TT (9) OC, to have an exodentate conformation in its free state, although the increased ring strain inherent in the o-xylyl group permits the ligand to convert to an endodentate conformation, permitting facial coordination at a metal atom. The ligand 5-oxa-2,8-dithia (9) -o-cyclophane, ODT (9) OC, may also coordinate to metal centres in a facial manner. Chapters 1 and 2 serve as …


Intraplatelet Abnormalities In Diabetes Mellitus., Arumugam. Muruganandam Jan 1994

Intraplatelet Abnormalities In Diabetes Mellitus., Arumugam. Muruganandam

Electronic Theses and Dissertations

Intraplatelet abnormalities in the platelets from diabetics have been evaluated with a view of understanding diabetes related platelet hyperaggregation. Three of the modulators involved in the platelet regulatory mechanism namely glutathione (GSH), calmodulin (CaM) and nitric oxide (NO) have been assessed in platelets from both normal and diabetic subjects. GSH and NO levels in the platelets from diabetics were lower ($\sim$50% & 57% respectively) when compared to platelets from normal subjects, whereas there was no change in the level of total CaM in platelets from diabetics. Estimates of steady state kinetic parameters (apparent K$\sb{\rm M}$ and apparent V$\sb\max)$ for the …


Iron Carbonyl-Mediated Michael Homologous Reactions Of Gamma-Alkoxy Alkenones., Tianhao. Zhou Jan 1994

Iron Carbonyl-Mediated Michael Homologous Reactions Of Gamma-Alkoxy Alkenones., Tianhao. Zhou

Electronic Theses and Dissertations

The reaction of $\gamma$-benzyloxy-$\alpha,\beta$-unsaturated ketones with diiron nonacarbonyl afforded the corresponding $\eta\sp2$-iron tetracarbonyl alkene complexes selectively, without perceptible formation of $\eta\sp4$-iron tricarbonyl complexes. In the presence of boron trifluoride-etherate, these complexes formed $\eta\sp3$-allyl tetracarbonyliron cation intermediates, which reacted with silyl enol ethers, silyl ketene acetals, allyltributyltin, and an electron rich arene to afford 59a-d, 59e, 59f, and 59g, respectively. The regiochemistry of the reactions was exclusively $\gamma$- with respect to the carbonyl, and the geometrical stability of the allyl tetracarbonyliron cation intermediates allowed retention of configuration of the double bond. The substrates, $\gamma$-benzyloxy-$\alpha,\beta$-unsaturated ketones (55a-c), were prepared from propargyl alcohols, …


Octa-Functionalization Of Calix(4)Resorcinarenes And The Complexation Of Metal And Ammonium Cations., John Robert. Fransen Jan 1994

Octa-Functionalization Of Calix(4)Resorcinarenes And The Complexation Of Metal And Ammonium Cations., John Robert. Fransen

Electronic Theses and Dissertations

Octa-functionalizations of C-heptyl- and C-undecylcalix (4) resorcinarenes were obtained by substitution reactions with $\alpha$-bromoacetates or $\alpha$-bromoacetamides. The association constants of cation binding of 3 a-c and 4 a-c were determined using alkali cations, (Na$\sp+$, K$\sp+$, Rb$\sp+$, Cs$\sp+$), alkaline earth cations, (Mg$\sp{2+},$ Ca$\sp{2+},$ Ba$\sp{2+}$), ammonium ions, (NH$\sb4\sp+,$ t-BuNH$\sb3\sp+$), silver(I) and lanthanum(III) cations by means of the picrate extraction technique via UV-VIS spectroscopy. The conformations of 3c and 3c $\cdot$ Ag$\sp+$ were determined to be flattened cone by variable temperature $\sp1$H NMR studies. Source: Masters Abstracts International, Volume: 34-02, page: 0764. Adviser: Philip J. Dutton. Thesis (M.Sc.)--University of Windsor (Canada), 1994.


Group Iv Transition Metal Complexes Of Phosphides And Phosphinidenes., Jianwei. Ho Jan 1994

Group Iv Transition Metal Complexes Of Phosphides And Phosphinidenes., Jianwei. Ho

Electronic Theses and Dissertations

ABSTRACT HAS BEEN ARCHIVED 07/12/97 Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1994 .H615. Source: Dissertation Abstracts International, Volume: 56-01, Section: B, page: 0233. Adviser: Douglas W. Stephan. Thesis (Ph.D.)--University of Windsor (Canada), 1994.


Genetics And Cellular Expression Of Human Apolipoproteins., Godwin Orji. Ogbonna Jan 1994

Genetics And Cellular Expression Of Human Apolipoproteins., Godwin Orji. Ogbonna

Electronic Theses and Dissertations

The purpose of this dissertation was to investigate the genetics and cellular expression of human apolipoproteins. The genetics aspect was an investigation of the Hind III apolipoprotein B gene DNA polymorphism and its association with lipids and lipoprotein parameters in a selected Canadian Caucasian population with documented coronary artery disease, and a healthy control population. To carry out this project, a simple and rapid method for the purification of human DNA from whole blood was developed. Typical 260 nm/280 nm absorbance ratio and yield for DNA so purified were 1.84 and 24.5 $\mu$g/mL, respectively. Patients had significantly (p $<$ 0.05) higher levels of cholesterol, triglycerides, LDL-cholesterol, apolipoprotein B, and lower level of apoAI compared to the controls. Restriction fragment length polymorphism analysis detected 9 hybridizable fragments denoted as H1 to H9. The H1, H2, H3, and H7 alleles were polymorphic. The (H4-H9) genotype was detected in 69% of the control group while the (H1-H9) genotype was observed in 68% of the patients. In the second phase of the studies the effects of insulin and thyroid hormone on apolipoprotein B, E, and AI mRNA expression were investigated using hepatoma cell-line. Thyroid hormone increased apolipoprotein B mRNA levels by about 25-36% as determined by slot- and Northern-blot analysis of total cellular RNA. No change in the amount of apolipoprotein B mRNA, measured by either slot- or Northern-blot analysis of total RNA was found in insulin treated cells. Both insulin and thyroid hormone were found to have no significant effect on apoE mRNA levels. The levels of apolipoprotein AI mRNA were found to be decreased by thyroid hormone and increased by insulin by about 19% and 30% respectively. A competitive chemiluminescent immunoassay was also developed for the sensitive measurement of apolipoprotein B. The lower limit of detection was 2.17 $\mu$g/L (4.0 pmol/L). Comparison of the assay with an immunoturbidimetric assay gave a slope of 0.84, y-intercept at $-$0.94 and a correlation coefficient of 0.86. In summary, the observed mutations in apolipoprotein B gene may not affect the rate of apolipoprotein B synthesis, clearance or the affinity of low-density lipoprotein for structural elements on the arterial wall. Furthermore, thyroid hormone appears to regulate apolipoprotein B and AI transcription while insulin modulates only apoAI mRNA levels.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1993 .O42. Source: Dissertation Abstracts International, Volume: 56-01, Section: B, page: 0223. Adviser: K. Adeli. Thesis (Ph.D.)--University of Windsor (Canada), 1994.


Hormonal Regulation Of Apolipoproteins Synthesis And Secretion In Human Hepatocytes., Andre G. Theriault Jan 1994

Hormonal Regulation Of Apolipoproteins Synthesis And Secretion In Human Hepatocytes., Andre G. Theriault

Electronic Theses and Dissertations

Faulty regulation of various apolipoproteins by the human liver may be an important contributor in the development of coronary heart disease. The factors that regulate hepatic apolipoprotein production are largely unknown. In cell culture, insulin appeared to reduce the secretion of apolipoprotein B, whereas thyroid hormone stimulated apolipoprotein B secretion. Both of these effects were found to be dose-dependent. In order to understand the mechanisms underlying the regulation of hepatic apolipoprotein B secretion, a cell-free translation system derived from a human hepatoma cell-line, HepG2, was developed to investigate the rate of apolipoprotein B synthesis. Extracts of HepG2 cells were found …