One microfiche--`Data from crystal structures solved by the author`--in pocket / Bibliography: leaves 172-174 / 174 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1987

Bibliography: leaves 317-318

M.W.P. Strandberg, T. Wentink, Jr. [and] A.G. Hill. / "June 21, 1948." / Bibliography: p. [14] / Army Signal Corps No. W-36-039-sc-32037.

M.W.P. Strandberg, T. Wentink, Jr. [and] R.L. Kyhl. / "May 13, 1948." / Bibliography: p. 17. / Army Signal Corps Contract W-36-039 sc-32037.

Diabetes mellitus is characterized by hyperglycemia, oxidative stress and excessive production of intermediary metabolites including methylglyoxal (MGO), a reactive carbonyl. MGO can readily interact with proteins, lipids and DNA, and cause an imbalance of the cellular antioxidant system leading to carbonyl stress. The effects of MGO can be devastating if the targeted molecules are responsible for the maintenance of membrane potentials and ionic homeostasis. Here we show that MGO disrupts the vascular isoform of ATP-sensitive K+ (KATP) channels by acting on the mRNAs of Kir6.1 and SUR2B subunits thereby regulating vascular tone. Our results show that the 3’ untranslated region (UTR) of Kir6.1 mRNA and the coding region of SUR2B mRNA are targeted by MGO causing a disruption of vascular KATP channels. The destabilization of the mRNAs of KATP channel can in turn affect K+ homeostasis of vascular smooth muscles as well as vascular responses to circulating vasodilators and vasoconstrictors.

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were also kinetically investigated. The low-reactive trans-dioxoruthenium(VI) porphyrin complexes (3a-b) were synthesized from the oxidation of their carbonylruthenium(II) porphyrin precursors with m-chloroperoxybenzoic acid (m-CPBA) and characterized spectroscopically by 1H-NMR, IR, and UV-vis. The low-reactivity of these complexes makes them suitable for kinetic studies. The sulfoxidation with the trans-dioxoruthenium(VI) species followed a pseudo-first order kinetic decay from RuVI to RuIV species with no accumulation of intermediates. The reactivity order in the series of dioxoruthenium(VI) complexes follows 3b > 3a >3c, which is consistent with expectations based on the electrophilic nature of high-valent metal-oxo species. Steric effect of the substituents on the complexes also affected the reactivity order. The kinetic results revealed that the sulfoxidation reaction with these well-characterized dioxoruthenium(VI) complexes is 3 – 4 orders of magnitude faster than the epoxidation reaction with the same complexes under similar conditions.

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Reactions of Fullerene with Tris(diphenylacetylene)(carbonyl)Tungsten and structure identified of these compounds. Due to its have many special mechanism for Tris(diphenylacetylene)(carbonyl)Tungsten. They could form interested structure of new compounds. Synthesis in high temperature we could get metallofullerene compounds W(CO)(£b2-C60)(£b2-PhC¡ÝCPh)(£b4-C4Ph4) 1a and W(CO)(£b2-C60)(¡ÝCPh)(£b5-C5Ph5) 1b. We also through C-H activation to get compound W(CO)2(£b3,£b5-C5Ph4(o-C6H4)CHPh) 2. To separate and Purify these compounds. To make sure mechanism of compound 2, we use cross experiment to confirm it.

The concentrations of atmospheric carbonyls were studied by the LpDNPH-Cartridge and the microcomputer air sampling device at Nanzi and Siaogang sites in Kaohsiung city. Source apportionment was determined by the factor analysis. The results showed that the highest concentrations of carbonyls was acetaldehyde (27.83 £gg/m3) at Nanzi, followed by formaldehyde (5.03 £gg/m3). At Siaogang, the highest concentrations of carbonyls was acetaldehyde (28.91 £gg/m3), followed by formaldehyde (6.92 £gg/m3). The concentrations of total carbonyls was higher at Siaogang (57.86 £gg/m3) than those at Nanzi (49.74 £gg/m3) . The concentrations of total carbonyls at Nanzi were 65.42 £gg/m3 in summer and 25.06 £gg/m3 in winter, and were 85.09 £gg/m3 in summer and 37.12 £gg/m3 in winter at Siaogang, due to the fact that summer has stronger photochemical activities than in winter. Additionally, peak rush hours of the traffics, either in the morning or at night, would result in increased concentration of Carbonyls was higher. The concentrations of atmospheric carbonyls were studied by the LpDNPH-Cartridge and the microcomputer air sampling device at Nanzi and Siaogang sites in Kaohsiung city. Source apportionment was determined by the factor analysis. The results showed that the highest concentrations of carbonyls was acetaldehyde (27.83 £gg/m3) at Nanzi, followed by formaldehyde (5.03 £gg/m3). At Siaogang, the highest concentrations of carbonyls was acetaldehyde (28.91 £gg/m3), followed by formaldehyde (6.92 £gg/m3). The concentrations of total carbonyls was higher at Siaogang (57.86 £gg/m3) than those at Nanzi (49.74 £gg/m3) . The concentrations of total carbonyls at Nanzi were 65.42 £gg/m3 in summer and 25.06 £gg/m3 in winter, and were 85.09 £gg/m3 in summer and 37.12 £gg/m3 in winter at Siaogang, due to the fact that summer has stronger photochemical activities than in winter. Additionally, peak rush hours of the traffics, either in the morning or at night, would result in increased concentration of Carbonyls was higher. Source apportionment analysis using factor analysis shows that the principle sources at Nanzi were traffic exhausts (motor, diesel, and gasoline vehicle) and stationary sources (industry, restaurant and chemical processes). The main sources at Siaogang were traffic exhausts (motor and gasoline vehicle), stationary sources (industry and restaurant) and secondary photo-chemical reactions.

The concentrations of atmospheric carbonyls were studied by the LpDNPH-Cartridge and the microcomputer air sampling device at Nan-Chie ¡BHsiung-Kong¡BRen-Wu and Lin-Yuan sites. Factor analysis was also used to determine the source apportionment in the Kaoshiung area. The results showed that the highest concentrations of carbonyls was acetaldehyde (27.83, 28.91, 11.46 and 10.06 £gg/m3) at four sites, followed by formaldehyde (5.03, 6.92, 7.88 and 6.59 £gg/m3), respectively. The highest concentration of total carbonyls at Nan-Chie and Hsiung-Kong was 65.42 £gg/m3 and 85.09 £gg/m3 in summer, the lowest concentration was 25.06 £gg/m3 and 37.12 £gg/m3 in winter, relatively, the highest concentration of total carbonyls at Ren-Wu and Lin-Yuan was 49.94 £gg/m3 and 55.24 £gg/m3 in winter, the lowest concentration was 24.48 £gg/m3 and 11.78 £gg/m3 in autumn. Additionally, peak rush hours of the traffics, either in the morning or at night, would result in increased concentration of Carbonyls. The results of factor analysis showed that the principle sources at Nan-Chie were traffic exhausts (diesel and gasoline vehicle) and stationary sources (metal assembly, waste treatment, pulp and restaurant). The principle sources at Hsiung-Kong were traffic exhausts (diesel, and gasoline vehicle), stationary sources (leather, chemical process and restaurant). The main sources at Ren-Wu were traffic exhausts (gasoline vehicle) and stationary sources (metal assembly, chemical process and restaurant). The main sources at Lin-Yuan were traffic exhausts (diesel vehicle) and stationary sources (metal assembly, leather, steel production and restaurant).