<p> This thesis describes an investigation into the effects of Lewis acid complexation on the photochemistry of α,β unsaturated carbonyl compounds.</p> <p> Initial studies involved the use of Nuclear Magnetic Resonance (NMR) and Ultraviolet (UV) spectroscopy in examining Lewis acid modification of the photostationary state for E/Z isomerization of various acyclic enones. The results obtained provide a good understanding of the origin of the perturbation of the photostationary state of these systems. In the course of these investigations, the question also arose as to the possible effects of complexation upon the photochemistry of cyclic enone systems where E/Z isomerization cannot occur, particularly whether this would catalyze [2+2] cycloadditions to the enone carbon/carbon double bond. Lewis acid complexed enones are widely used as activated dienophiles in Diels Alder reactions, and have been recently reported to serve as activated 'enophiles' in a photochemical dimerization of coumarin.</p> </p> The examination here is focused upon endo-tricyclo [5.2.1.02,6] deca-4,8-dien-3-one. (See Diagram in thesis). </p> <p> Reported here is a detailed investigation of the photochemistry of the AlEtCl2 complex of this compound, and the results are interpreted mechanistically. The reaction gives rise to a single product which reaches a photostationary state with the reactant complex. The isomerization is formally a [1,3] sigmatropic shift involving the isolated double bond. It seems likely however, to proceed by the formation of an allyl cation intermediate.</p> / Thesis / Master of Science (MSc)

<p> The photochemistry of 1,1-diphenylsilacyclobutane has been studied by steady-state and nanosecond laser flash photolysis (NLFP) techniques in order to investigate the mechanism of reaction of a transient silene with alcohols. NLFP of 1,1-diphenylsilacyclobutane (I) in acetonitrile solution at 325 nm results in the formation of 1,1-diphenylsilene (II) derived from excited-state [2+2]-cycloreversion of the silacyclobutane. The transient has a lifetime of 100 ns - 1.2 μS in acetonitrile solution at room temperature, depending on the presence of water in the solvent. Steady-state photolysis in the presence of various σ-bonded nucleophiles such as methanol results in the generation of a single product in each case, consistent with addition of the nucleophile to the silene (II). Absolute rate constants (kq) have been determined by NLFP techniques for reactions of the silene with water, methanol, ethanol, tert-butyl alcohol, 2-propanol, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoroisopropanol, and glacial acetic acid. The rate constants (kq) illustrate the following characteristics: linear quenching plots characteristic of second order kinetics, observation of small but detectable deuterium kinetic isotope effects, and an inverse Arrhenius temperature dependence. Two possible mechanisms will be discussed based on these results. (See Mechanisms in Thesis)</p> / Thesis / Master of Science (MSc)

<p> 1,1-Diarylindenes rearrange when heated or irradiated to give 1,2- and 2,3-diarylindenes. Three 1,1-diarylindenes were synthesized and used in an attempt to probe the transition states for phenyl migration in both the ground and excited state. The three indenes synthesized were: 1-(p-bromophenyl)-1-phenylindene, 1-(p-cyanophenyl)-1-phenylindene and 1-(p-methoxyphenyl)-1-phenylindene.</p> <p> On direct irradiation, the migratory aptitudes were -C6H4CN-p, 98%; -C6H4OCH3-p, 95%; and -C6H4Br-p, 86%. On heating (258°C) the following aptitudes were found: -C6H4CN-p, 82%; -C6H4OCH3-p, 48%; and -C6H4Br-p, 53%. The products were synthesized independently, and the product ratios obtained upon reaction were measured from the n.m.r. of mixtures, and by v.p.c. A charge transfer mechanism was put forward to explain the preference for migration of the substituted group in the excited state. Such charge transfer contributions are known to increase the rates of quenching in donor-acceptor pairs. A radical-type transition state was postulated as being present in the ground state migration. The rate constant for excited state rearrangement was calculated to be 4.9 x 10^9 sec^-1 .</p> / Thesis / Doctor of Philosophy (PhD)

Waveguide architectures were inscribed within two different stimuli-responsive hydrogels capable of actuation. An electroactive hydrogel, which deforms when placed within an electric field, is demonstrated as a method for remote actuation and steering of light outputs. Lattices of waveguide with diameters on the microscale were embedded within hydrogel prisms, achieved through a nonlinear light propagation process known as self-trapping. This process is a result of balance between the natural divergence of light and self-focusing effects caused by an irreversible positive refractive index change during photopolymerization. Waveguiding structures are inscribed in the material because of this process. Square (2D) and near-cubic (3D) lattices were inscribed in hydrogel prisms, demonstrating the ability to remotely steer one or two light outputs simultaneously using an electric field. The overall optical effect is reminiscent of camouflaging techniques observed in marine creatures (ie. cephalopods). Additionally, a novel volumetric 3D printing technique previously demonstrated by the Saravanamuttu group was implemented to fabricate hydrogel cylinders capable of photothermal actuation. Coupling a thermoresponsive hydrogel material with a photoabsorber, areas irradiated by a light source are observed to contract. These contractions lead to the deflection of waveguiding cylinders towards the light source, reminiscent of the phototropic behaviours observed in particular plants (ie. sunflowers). The results of these studies provide insight for the fabrication of functional materials through nonlinear light propagation. Understanding these systems could provide knowledge for the fabrication of other stimuli-responsive materials with light-guiding properties. / Thesis / Master of Science (MSc)

Chloroplasts of sugar beet leaves were subjected to treatment by heating, by incubation at pH 8.5 and pH 5.5, by incubation in ion low water, by sonic oscillation, by digestion with enzymes (lysozyme, pancreatin, and lipase), by extraction with digitonin, and by chemical compounds including 8-hydroxy-quinoline, sodium azide, zinc sulfate, phenyl mercuric acetate, potassium cyanide, 1-allylthiourea, 2,4-dinitrophenol, thymol, and p-chloromercuribenzoate. A comparative study was made of the effects of these treatments upon three photochemical reactions (the photoreduction of 2,6- dichlorophenol indophenol, the photoreduction of indigo carmine in the presence of a couple composed of 2,6-dichlorophenol indophenol and ascorbic acid, and the photo-oxidation of the 2,6-dichlorophenol indophenol-ascorbic acid couple) and upon three enzymes (cytochrome oxidase, peroxidase, and catalase) present in the chloroplast preparations used.

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