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<p> This thesis presents the theoretical study of the mechanisms of gas-phase formamide hydrolysis using ab initio SCF-MO calculations. Four reaction paths were considered; (i) the reaction of formamide with OH- (ii) the acid catalyzed hydrolysis with protonation on the nitrogen atom (iii) the acid catalyzed hydrolysis with protonation on the oxygen (iv) the uncatalyzed hydrolysis. An unconstrained optimization of all parameters was performed on the transition state and equilibrium structures. The intrinsic reaction coordinate was then followed down from the transition state to the reactants and products. All of the molecular geometries were obtained using the 4-31G basis set and all wavefunctions and energies were calculated at the 6-31G** level of theory. The theory of atoms in molecules was applied to each reaction to study the mechanisms of structural change along the reaction coordinate. Molecular graphs were calculated at points along the reaction coordinate and these give a detailed pictorial outline of the entire reaction sequence. The Laplacian of the charge density successfully predicts the correct site of protonation and the enhanced reactivity of protonated formamide over that of neutral formamide. Both the acid catalyzed reaction with nitrogen protonation and the base enhanced hydrolysis reactions proceed without a barrier with respect to reactants and products. The acid catalyzed hydrolysis with protonation on the oxygen atom proceeds with a moderate activation barrier whereas the neutral hydrolysis involves the passage over a very high activation barrier. The two acid catalyzed reactions are competitive with the N-protonation mechanism being more favourable from a kinetic point of view while the O-protonation mechanism is thermodynamically more favourable.</p> / Thesis / Master of Science (MSc)

<p> Several ketones in the bicyclo{2.2.1.}heptane system, many of them previously unknown, have been prepared and characterized; these included monoketones, enones and diones. They are listed in Fig. II-1.</p> <p> The conformations of norbornane-2,5-dione (27) and 3,3-dimethyl-norbornane-2,5-dione (26) have been carefully examined by nuclear magnetic resonance spectroscopy. These compounds have been found to exist in two different synchro twist conformations.^76</p> <p> The stereochemistry of base-catalyzed protium-deuterium exchange of the diones 25, 26 and 27 has been examined and has been found to be similar to the stereochemistry of exchange in monoketones previously observed in these systems, viz exo exchange is considerably more rapid than endo exchange.</p> <p> The rates of NaOD-catalyzed protium-deuterium exchange of the ketones, enones and diones have been measured in 60 % dioxane-D2O at 25°. The rate data is shown in Table II-4. Kinetic analysis showed that these rate constants represent the true reactivity of the hydrogen for which the rate of exchange was measured.</p> <p> A study of the 13C chemical shift of highly substituted bicyclo{2.2.1.}heptanes has been undertaken, and also a study of the 13C-H coupling constants of many of these compounds has been made. The results are listed in Tables II-6 and II-8. They suggest that there are no unusual hybridization effects at the enolizable carbon in the diones and enones under study.</p> <p> The rate data, together with some literature data, shows that hybridization effects, torsional effects, conformational effects and strain effects are of minor importance in the exchange reactions. The rate acceleration observed in the dione systems is almost entirely accountable by an inductive effect of the second carbonyl group, with very little homoconjugative participation.</p> <p> The kinetic results suggest that an enol is the intermediate in the enolization reaction, and that the transition state occurs relatively early along the reaction coordinate.</p> / Thesis / Doctor of Philosophy (PhD)

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No description available.

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No description available.

<p> AlkA is a monofunctional DNA glycosylase from E.coli. This enzyme catalyzes the hydrolysis of the N-glycosidic bond, initiating the first step in the base excision repair pathway. This activity is crucial to the maintenance of the genetic code, as the persistence of DNA aberrations can have significant cellular consequences including mutation, and inhibition of DNA replication and transcription. This enzyme has a broad substrate specificity catalyzing the excision of various lesions (including alkylation, oxidation and deamination products) from DNA. While biochemical and structural studies have been carried out on AlkA; how this enzyme is able to recognize and excise a variety of structurally diverse lesions from DNA and the mechanism by which this excision occurs remains unknown. In this study we have shown that a stem-loop DNA structure containing a hypoxanthine bulge is an optimal substrate for TS analysis of AlkA-catalyzed N-glycoside hydrolysis. In addition, we have developed methods to synthesize radiolabeled deoxyinosine triphosphate (diTP) and incorporate this radiolabeled nucleotide into the stem-loop DNA structure. We have developed a facile method of purification for his-tagged AlkA and his-tagged AlkA containing a TEV protease recognition site (for removal of the his-tag), and have shown that these proteins display an activity similar to that of wild-type AlkA. The [1'-3H] KIE was measured using liquid scintillation in a proof-of-principle experiment. The observed value of 1.046 is indicative of either a relatively synchronous ANDN (SN2) TS or an early DN*AN (SN1) TS with oxacarbenium ion character in the sugar ring, but significant bond order to the leaving group base still remaining. Future work involves repeat measurements of the [1 '-3H] KIE to validate the accuracy of the measurement observed here, examination of commitment to catalysis and optimization of the hypoxanthine bulge substrate synthesis. Analysis of KIEs at additional sites on the hypoxanthine base and sugar ring will contribute to TS analysis of AlkA-catalyzed N-glycoside hydrolysis and help elucidate the mechanism of hydrolysis. </p> / Thesis / Master of Science (MSc)

<p> The foaming process has received increased attention by the rotational molding industry in recent years. The use of metallocene catalyzed polyethylenes for producing a cellular structure is a new development in rotational molding. The objective of this work was to investigate the effects of different chemical blowing agents, resin properties and processing conditions on the structure of foamed metallocene polyethylene and obtain a fundamental understanding of the parameters governing the foam structure and part properties.</p> <p> An experimental study was conducted to produce metallocene polyethylene foams in dry-blending-based rotational foam molding. The physical and cell structure properties of the final foamed parts were examined. The critical processing parameters that optimize the foam structure have been identified through adjustments to the molding conditions.</p> <p> The foaming performance of exothermic and endothermic chemical blowing agents were examined and it was revealed that selecting an appropriate chemical blowing agent was crucial as the foam structure depends significantly on the properties of the blowing agent. Exothermic blowing agents resulted in greater foam density reduction compared to endothermic blowing agents.</p> <p> The effect of rheological properties on the foaming process and foam properties was also examined. Rotomolding experiments were performed in monolayer and skin-foam moldings. Observations indicated that the final foam properties were profoundly influenced by the rheological properties of the polymer materials. There was a good correlation between the foam properties produced in both monolayer and two layer moldings. It was discovered that polymer materials with higher extensional viscosity could provide a promising foaming performance at different processing conditions.</p> <p> The effect of the surface tension of the polymer materials was investigated. It was found that type of reaction of the blowing agent (exothermic/endothermic) and composition of gas generated determine whether the surface tension of the resin contributes to the trend of changes in foam properties.</p> / Thesis / Master of Applied Science (MASc)

The versatility of organoboron compounds has been demonstrated by their use as synthetic intermediates and more recently in therapeutic applications since the FDA approval of Velcade©. As a result, transition metal-catalyzed protocols to incorporate boron reagents into unsaturated compounds have been extensively researched. While an abundance of literature protocols have been reported, the majority utilize harsh reaction conditions in combination with expensive reagents. This dissertation discloses the author’s contributions to the development of efficient, cost-effective, and operationally simple transition metal-catalyzed borylation protocols with alkynes and diboron reagents. An open-to-air copper(II)-catalyzed aqueous borylation protocol of alkynoates and a symmetrical diboron reagent is reported. Conjugate addition of the boryl-copper species to the electrophilic β-carbon provided β-boryl-α,β-unsaturated esters in moderate to excellent yields. Exclusive (Z)-stereochemistry was confirmed by nOe experiments. The resulting vinyl boronate esters are useful cross-coupling partners. The scope of the aqueous β-borylation protocol was extended to the unsymmetrical diboron reagent, pinB-Bdan. This alternative protecting group has emerged as an orthogonal protecting group and alters the reactivity of the boron moiety. Activation of the pinacol moiety to form the Lewis acid-base adduct allowed for the chemoselective transfer of the 1,8- diaminonapthalene moiety to the β-carbon. An alternative novel synthesis of vinyl, allyl diboronate esters from propargylic alcohols has also been described. Formation of a leaving group in-situ with a palladium- and coppercatalyzed protocol can lead to several competing reaction pathways and the formation of multiple products. Fortunately, the resulting vinyl, allyl diboronate esters were stereoselectively synthesized in moderate GC yields despite significate decomposition during purification, as confirmed by stability studies. The terminal diboration of allenes was previously the only reported method for the synthesis of vinyl, allyl diboronate esters. / Ph. D.