In the last decade photoredox catalysis has emerged as an important new tool for organic chemists. The especially mild conditions and the broad range of reactions accessible using this methodology had a beneficial effect on the exploitation of radical reactions on otherwise labile substrates. Herein we report our work in this fast developing area and our efforts into the double functionalisation of styrenoid double bonds. We disclosed a new methodology for the room temperature photoredox catalysed alkoxy- and amino-arylation of styrenes using diaryl iodonium tetrafluoroborates and diazonium salts as aryl radical precursors. This methodology allows the successful regioselective coupling of three disparate components together and can be expanded to a wide range of alcohol nucleophiles, nitriles and water in moderate to good yields. The mild conditions employed permit the effective reaction of electron-rich styrenes and the tolerance of halogen functionalities, thus opening the possibility to further molecular elaboration. We then moved to explore the possibility of oxymethylnitrilation of styrenes and of the sysnthesis of heterocyclic cores via internal trapping with a nucleophile. Pleasingly, we were able to develop a mild and general methodology for the methylnitrilation of styrenes using simple and cheap bromoacetonitrile and photoredox catalysis. Furthermore, the synthesis of tetrahydrofuran and dihydrofuran cores was achieved in a single step, allowing us to synthesise tricyclic cores, maintaining functionisable handles such as halogens and ester groups. Finally, we decided to explore the possibility to add an azide functionality. After extensive optimisation, we were pleased to discover reaction conditions allowing for a switchable reactivity: under light irradiation we could perform an azidation reaction followed by addition of a nucleophile of choice; excluding the light from the reaction conditions, we could perform a double azidation reaction. The mild reaction conditions ensured the previously observed tolerance of functional groups; furthermore, we used a more sustainable copper-based photoredox catalyst.

Fideism, or basing one’s religious belief on faith, is popular especially amongst modern Protestant Christians. For the fideist, religious belief-systems are not subject to rational evaluation, and faith as the act of belief forms the essence of truth and the ultimate criterion for embracing a religion. Critics of fideism say that epistemologically, a hierarchy of methods can be used to derive the truth, and each method gives us varying confidence levels. These methods include mathematics and logic, science, personal experience, history, expert testimony, inference and Faith. Among these, the critic says, pure faith in something is the least successful in getting at the truth. Radical fideists like Kierkegaard do not cite logical reasons for defending their belief that God exists. Personal reasons are instead offered for their decision to believe. In this thesis I seek to demonstrate that the radical fideism advocated by Kierkegaard constitutes good justification for belief in the Christian God. I will begin with a discussion on fideism and some of its proponents, followed by a discussion on the place of faith (as a non-rational belief in God’s existence) in religion. I will then appeal to Kierkegaard’s philosophy in defending my view that religious belief in God is a matter of faith and personal commitment, feeling and passion, and this is an inner process not grounded in arguments. References will be drawn from Kierkegaard’s themes of faith, subjectivity and inwardness. I conclude by saying that even if no objective grounds exist to justify our belief, Kierkegaard standpoint remains right in two ways: Firstly, the fideist rejection of the attempt to justify his belief through offering reasons for it is precisely what makes his decision to believe deeply meaningful in his life. Secondly, those who ‘try to judge faith by objective, critical reflection will go on forever that way, and will never reach the point of having faith and of being religious’. (Peterson et al, 2003:53)

Thesis (Ph.D.) -- McMaster University, 2007. / Supervisor: Shiping Zhu. Includes bibliographical references.

The first chapter of this thesis represents the continued development of a general method for the formation of benzo-fused N-heterocycles by formal radical cyclization onto benzene rings. Important stages in this process involve 1) the copper-mediated coupling of various amino alcohols to protected p-iodophenols, 2) carbamate-protection of the resulting aryl secondary amine to allow the following oxidation step, 3) the oxidative formation of quinone ketals as radical acceptors, 4) the radical cyclization of pendant iodo-radical triggers onto the cross-conjugated ketone, and 5) the subsequent aromatization of the resulting products into benzo-fused N-heterocycles. Various protected 2,3-dihydroindolessome of which with 2-substitutionshave been synthesized using this methodology. For some examples, it was necessary to repeat the experiments of a previous group member to obtain publication-quality data. The second chapter describes a new methodology for the formation of regioselectively-substituted benzene rings. Various arene species have been synthesized in p-disubstituted, 1,2,4-trisubstituted and 1,2,3,4-tetrasubstituted arrays. Key steps in the methodology include 1) the synthesis of 1,4-diketones by alkylation of various aldehydes and their subsequent reduction and oxidation, 2) addition of organometallic alkenes to 1,4-diketones to form ring closing metathesis (RCM) precursors, and 3) RCM and subsequent aromatization of these cyclized products by double-dehydration to form the desired substituted benzenes. The macrocycle [12]-paracyclophane has also been synthesized using a modified version of the above methodology.

Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures. In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose. Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.

<p>&nbsp / </p> <p align="left">The main aim of this study was to design new polyfunctional ligands based on the polypropyleneimine dendrimer&nbsp / <font face="Arial">DAB-(NH</font><font face="Arial" size="1"><font face="Arial" size="1">2</font></font><font face="Arial">)</font><font face="Arial" size="1"><font face="Arial" size="1">4 <font face="Arial">referred to as </font><b><font face="Arial,Bold">L1 </font><font face="Arial">in this work, to be used in </font></b></font></font><font face="Arial">copper mediated atom transfer radical polymerization (ATRP) of vinyl monomers. These ligands were synthesized by modifying DAB-(NH</font><font face="Arial" size="1"><font face="Arial" size="1">2</font></font><font face="Arial">)</font><font face="Arial" size="1"><font face="Arial" size="1">4 </font></font><font face="Arial">with aromatic and aliphatic substituents on the nitrogen atoms at the periphery of </font><b><font face="Arial,Bold">L1</font><font face="Arial">.</font></b></p>

Recently, controlling the shape of nanoparticles during their fabrication has become a new and interesting research area. In fact, the nanoparticle has been proven that its physical properties are strikingly related to the shape of itself. After finding the carbon nanotubes in 1911, more and more nanostructure materials have been synthesized. The radical nano-scale vanadium oxide VO2.24(C12H14N2)0.061 is synthesized by hydrothermal method. VO2.24(C12H14N2)0.061 has various physical properties, and we would focus on it¡¦s magnetic properties in the thesis, including magnetic susceptibility and magnetization. The magnetic susceptibility measurements show that the antiferromagnetic transition occurs at T = 20K ~ 25K, and it has been found the specific transition at T = 265K ~ 275K in some samples. Based on the magnetization data, these materials are ferromagnetic, and the hysteresis loops exhibit unusual steps. Whenever these materials process thermal treatments or not, the steps still exist. In addition, we will analyze the impact of the production date, thermal treatment, and preserved environment to discover more colorful properties of these materials.

The Amaryllidaceae class of alkaloids have been isolated from various species of Amaryllidaceae. In intramolecular radical cyclization, we used three methods to synthesize Amaryllidaceae.

<p>Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures.</p><p>In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose.</p><p>Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.</p>

Recent literature in the social sciences has emphasized the socially constructed nature of knowledge. Consequently, this has had a bearing upon the understanding of science; interpretations of the natural world; and issues associated with understanding 'the Other'. The relevance of these wider social debates can be extended into a consideration of 'natural' hazards in different cultural contexts. This thesis attempts to develop a 'middle ground', drawing on theories of critical realism, that appreciates the socially constructed nature of scientific practice, but that retains the empancipatory, positive potential of science and that allows intervention in other cultural contexts. The remainder of the thesis attempts to put some of these ideas into practice and to develop the implications of these arguments for those interested in understanding and mitigating 'natural' hazards in other cultures. Two case studies are used, relating to Egypt and the U.K., which explore the scientific understandings of 'natural' hazard events in two different cultural contexts. Fundamental to the approach adopted is the need to acknowledge science as a social practice and how it functions within different societies. Examples are given, pertaining to both Egypt and the U.K., of what this might mean in 'practice'. In summary, therefore, there is an appreciation of the implications of recent social science literature for hazards research and the development of a practical approach to hazards with a social and philosophical justification