The syntheses and characterization of nickel complexes; investigation of Ni(dppp)2 and [NiX(dppp)n]x, potentially catalytically active nickel(0)/(I) species for cross-coupling reactions

This thesis describes an investigation in which we compare Ni(0), Ni(I) and Ni(II) complexes containing 1,3-bis(diphenylphosphino)propane (dppp) as a phosphine ligand for their abilities to effect three types of cross-coupling reactions: Buchwald-Hartwig Amination, Heck-Mizoroki, and Suzuki-Miyaura cross-coupling reactions with different types of substrates. The Ni(0) complex Ni(dppp)2 is known and we have synthesized it via a new procedure involving zinc reduction of the known NiCl2(dppp) in the presence of an excess of dppp. The Ni(0) complex was characterized by NMR spectroscopy and X-ray crystallography. Since Ni(I) complexes of dppp seem unknown, we have synthesized what at this stage appear to be NiXdpppn/[NiX(dppp)n]x (X = Cl, Br, I; n = 1,2, x = 1, 2) by comproportionation of molar equivalents of Ni(dppp)2 and NiX2dppp, X= Cl, Br, I.

Condensed phase combustion travelling waves with sequential exothermic or endothermic reactions

The one-dimensional propagation of a combustion wave through a premixed solid fuel for two-stage kinetics is studied. We re-examine the analysis of a single reaction travelling-wave and extend it to the case of two-stage reactions. We derive an expression for the travelling wave speed in the limit of large activation energy for both reactions. The analysis shows that when both reactions are exothermic, the wave structure is similar to the single reaction case. However, when the second reaction is endothermic, the wave structure can be significantly different from single reaction case. In particular, as might be expected, a travelling wave does not necessarily exist in this case. We establish conditions in the limiting large activation energy limit for the non-existence, and for monotonicity of the temperature profile in the travelling wave.

Synthesis of profluorescent isoindoline nitroxides via palladium-catalysed Heck alkenylation

The synthesis of a new structural class of isoindoline nitroxides (aminoxyls), accessible via the palladium-catalysed Heck reaction, is presented. Reaction of the aryl bromoamine, 5-bromo-1,1,3,3-tetramethylisoindoline (4) or dibromoamine, 5,6-dibromo-1,1,3,3-tetramethylisoindoline (5) or the analogous bromonitroxides 6 and 7 with methyl acrylate gives the acrylate substituted tetramethylisoindoline amines 8 and 10 and nitroxides 12 and 14. Similarly, the reaction of the aryl bromides and dibromides 4–7 with methyl 4-vinylbenzoate gives the carboxystyryl substituted tetramethylisoindoline amines 9 and 11 and the analogous nitroxides 13 and 15. The carboxystyryl tetramethylisoindoline nitroxides demonstrate strongly suppressed fluorescence, which is revealed upon removal of the free radical by reduction or radical coupling.

Towards a cognitive-behavioural intervention for adult grief reactions

Published accounts of behavioural interventions for grief have relied on exposure and habituation to grief cues as the primary strategy. Such an approach is excessively narrow, since it does not adequately confront the challenges that are posed by a bereavement. Many people cope with a bereavement by themselves, and for those, intervention may well be counterproductive. A cognitive-behavioural intervention, following models for depression/anxiety, can assist vulnerable individuals obtain a more rapid or complete adjustment. The proposed approach differs from dynamic treatments by placing less emphasis on defensive behavior, insight, and interpretation and more emphasis on training of coping skills.

The psychological management of adult grief reactions

Despite the severe challenges which are posed by the loss of a close friend or relative, bereavement has a relatively benign outcome in most cases. While the majority of patients cope with bereavement, a significant minority develop problems. A behavioural approach may help the bereaved avoid adverse grief reactions.

Australian student reactions to U.S. tourism advertising : a test of advertising as public diplomacy

A study among Australian college students gauged their reactions to a television commercial produced for the U.S. Commerce Department to bolster sagging tourism numbers among international visitors. In addition to using traditional measures applied to tourism advertisements, the student also concluded items to measure attitudes toward the U.S. government and its people Pre- and post-viewing results indicated that while the Hollywood-movie-themed commercial was not well received by the Australian students as a tourism message, it did result in more favorable attitudes toward the U.S. government, though not the U.S. people. The findings lend partial support for the potential of tourism advertising efforts to exert a "bleed-over effect" in terms of their contributions to overall attitudes toward a country, regardless of whether viewers plan to visit the country whose travel advertisements they see.

Australian student reactions to US tourism advertising : a test of advertising as public diplomacy

A study among Australian college students gauged their reactions to a television commercial produced for the US Commerce Department to bolster sagging tourism numbers among international visitors. In additional to using traditional measures applied to tourism advertisements, the study also included items to measure attitudes toward the US government and its people. Pre- and post-viewing results indicated that although the Hollywood-movie-themes commercial was not well received by the Australian students as a tourism message, it did result in more favourable attitudes toward the US government, although not the US people. The findings lend partial support for the potential of tourism advertising efforts to exert a 'bleed-over effect' in terms of their contribution to overall attitudes toward a country, regardless of whether viewers plan to visit the country whose travel advertisements of which they see.

Interventions for preventing and managing radiation-induced skin reactions in cancer patients (Protocol)

To assess the effects of any interventions which aim to prevent or manage radiation-induced skin reactions in people with cancer.

Highly efficient, stoichiometric radical exchange reactions using isoindoline profluorescent nitroxides

Exchange reactions between the isoindoline profluorescent nitroxide 1,1,3,3-tetramethyldibenzo[e,g]isoindolin-2-yloxyl (TMDBIO) and a TEMPO capped polystyrene were carried out. High conversions to the desired products were achieved using only stoichiometric ratios of nitroxide relative to polymer. The scope of this study was expanded by exploiting a di-nitroxide 9,10-bis(5-[1,1,3,3-tetramethylisoindolin-2-yloxy])anthracene (BTMIOA) as a connector between two polymer chains forming PS–nitroxide–PS systems.

New palladium catalysed reactions of bromoporphyrins: synthesis and crystal structures of nickel(II) complexes of primary 5-aminoporphyrin, 5,5’-bis(porphyrinyl) secondary amine, and 5-hydroxyporphyrin

Primary aminoporphyrin, secondary bis(porphyrinyl)amine and hydroxyporphyrin complexes have been isolated and characterised both spectroscopically and crystallographically from the reaction of 5-bromo-10,15,20-triphenylporphyrinato-nickel(II) with hydrazine under palladium catalysis.

Teachers' and education students' perceptions of and reactions to children with and without the diagnostic label 'ADHD'

Thirty-four elementary school teachers and 32 education students from Canada rated their reactions towards vignettes describing children who met attention-deficit/hyperactivity disorder (ADHD) symptom criteria that included or did not include the label “ADHD.” “ADHD”-labeled vignettes elicited greater perceptions of the child's impairment as well as more negative emotions and less confidence in the participants, although it also increased participants' willingness to implement treatment interventions. Ratings were similar to vignettes of boys versus girls; however, important differences in ratings between teachers and education students emerged and are discussed. Finally, we investigated the degree to which teachers' professional backgrounds influenced bias based on the label “ADHD.” Training specific to ADHD consistently predicted label bias, whereas teachers' experience working with children with ADHD did not.