Magister Artium - MA / Backpacker tourism is a niche market of tourism that has been rapidly growing, South Africa in particular has become an increasingly popular destination for backpacker tourism (Visser 2004). Academic interest in backpacker tourism research has grown in recent years, although the current literature on backpacker tourism has focused on the economic significance and impacts with little empirical research conducted on the characteristics, motivations and behaviors. Cohen (2003) stresses that future research should stop referring to backpacking as if it were a homogeneous phenomenon, and should rather focus on its diverse manifestations in terms of origins, age, gender, class, nationality and cultural backgrounds of backpackers. Since backpacker tourism is a growing market it is important for the destination to understand the specifics and capabilities of the market in order to create sustainable products. The main aim of this research is to segment the backpacker tourism market in South Africa, in order to ascertain if any significant sub-groups exist. Both qualitative and quantitative methods were utilised to collect data including a distribution of 202 questionnaire surveys to backpackers within backpacker hostels and also participant observation was employed to gain an in-depth understanding of the phenomena. Factor and cluster analysis was used to analyse the data. The following motive-based segments were identified: Self-developers/ Learners, Experience Seekers, Escapers/ Independence, Adventures/ Social Seekers. The results revealed that these segments do illustrate an increase in the heterogeneity of backpacker tourism. The reason these sub-groups of backpackers are depicted in South Africa is to address the underlying desires of backpackers in order to satisfy their needs.

Ce travail s'inscrit dans le cadre de la chimie des carbènes N-hétérocycliques (NHC) et s'articule autour de la fonctionnalisation directe de l'hétérocycle des l'imidazol-2-ylidènes par substitution formelle d'un ou deux groupements diméthylamino. Deux nouvelles catégories de NHCs ont d'abord été obtenues par cette stratégie, dénommées 4-(diméthylamino)imidazol-2-ylidène IArNMe2 et 4,5-bis(diméthylamino)imidazol-2-ylidène IAr(NMe2)2. Les sels d'imidazolium précurseurs de ces NHCs, à savoir le triflate de 4-(diméthylamino)imidazolium (IArNMe2)·HOTf et le triflate de 4,5-bis(diméthylamino)imidazolium (IAr(NMe2)2)·HOTf, ont été synthétisés en couplant la formamidine disubstituée correspondante avec le N,N-diméthyl-chloroacétamide et le 1,2-dichloro-1,2-bis(diméthylamino)éthylène généré in situ respectivement. La quantification des propriétés électroniques des deux nouveaux NHCs a été réalisée à l'aide des complexes de type [Rh(IMes(NMe2)xCl(CO)2], montrant que la donation électronique des ligands NHCs augmente séquentiellement par la décoration avec un ou deux groupements diméthylamino, tandis que les propriétés de p-rétrodonation des NHCs ne sont que légèrement influencées. Par la suite, les complexes de palladium Pd-PEPPSI-IPrNMe2 et Pd-PEPPSI-IPr(NMe2)2 (PEPPSI : Pyridine Enhanced Preparation Purification Stabilization and Initiation) ont été préparés par des voies de complexation classiques. Les propriétés stériques des ligands a été évaluée par la mesure du pourcentage de volume occupé (%Vbur), et il est apparu que les propriétés stériques de ces deux nouveaux ligands NHCs sont également accrues. Les activités catalytiques des deux pré-catalyseurs ont été évaluées en amination de type Buchwald-Hartwig et comparées avec celle de la référence Pd-PEPPSI-IPr. Le pré-catalyseur Pd-PEPPSI-IPr(NMe2)2 s'est révélé le plus actif en amination des chlorures d'aryle à température ambiante. Il constitue également le catalyseur Pd-NHC le plus efficace et le plus général connu à ce jour en permettant de réaliser l'amination des chlorures d'aryle avec une charge de catalyseur très faible (jusqu'à 50 ppm), ou à l'aide d'une base faible telle que le carbonate de césium, et même d'activer les tosylates d'aryle, substrats beaucoup plus difficiles que les chlorures d'aryle . Afin de rationaliser au mieux les effets observés en catalyse en termes de propriétés stéréoélectroniques des ligands NHCs, le squelette arrière aminé des imidazol-2-ylidènes a été dérivatisé plus avant, soit en augmentant la contrainte stérique du groupe NMe2 dans IAr(NMe2) en ciblant le ligand IAr(NiPr2), soit en remplaçant formellement un des groupes amino par un groupe éléctro-attracteur tel un halogène dans le ligand IAr(NMe2)2. Alors que le sel d'imidazolium (IArNiPr2)·HOTf a été synthétisé suivant la même méthode que (IArNMe2)·HOTf, l'halogénation oxydante du squelette d'arrière de (IArNMe2)·HOTf par du NCS ou du NBS a donné les sels (IArNMe2, X)·HOTf avec de très bons rendements dans des conditions très douces. Il convient de noter que cette réactivité originale a été également observée sur les complexes de rhodium(I) et le palladium(II) du ligand IAr(NMe2). Les influences électroniques et catalytiques de ces modifications ont été étudiées de la même façon. / This work is incorporated within the framework of the chemistry of N-Heterocyclic Carbenes (NHCs) and aims at functionalizing the skeleton of imidazol-2-ylidenes by attachment of one or two amino groups. Two new NHC classes were first obtained by this strategy, namely the 4-(dimethylamino)imidazol-2-ylidene IArNMe2 and the 4,5-bis(dimethylamino)imidazol-2-ylidene IAr(NMe2)2. The synthesis of the precursors of these NHCs, the 4-(dimethylamino)imidazolium triflates (IArNMe2)·HOTf and the 4,5-bis(dimethylamino)imidazolium triflates (IAr(NMe2)2)·HOTf is based on the coupling between the corresponding disubstituted formamidine and either an a-chloroacetamide for the mono-amino derivative or a reactive dichlorodiaminoethene for the bis-amino analogue. The electronic properties of the resulting new NHCs ligands have been studied by measurement of their Tolman Electronic Parameter (TEP) values obtained from the IR spectra of the complexes [Rh(IMesXY)Cl(CO)2] and by 77Se NMR spectroscopy of their corresponding selenoureas [(IMesXY)=Se]. It was shown that the electronic donation of the carbenic carbon sequentially increases by decoration with one or two amino groups respectively whereas the p-accepting properties of the NHC are only slightly or even not affected by the adjunction of the NMe2 groups on the imidazolyl backbone. Later, the synthesis of the two new PEPPSI-type palladium pre-catalysts PEPPSI-Pd-IPrNMe2 and Pd-PEPPSI-IPr(NMe2)2 were successfully achieved. From the calculated the percent buried volume %Vbur which is related to the steric properties of the two supporting NHC ligands, it appeared that grafting one amino group onto the backbone already leads to significant improvement of steric congestion while the second amino only results in a slight increase of the steric issue. The catalytic efficiencies of both pre-catalysts were evaluated in the benchmark Buchwald-Hartwig amination and compared with this of the reference PEPPSI-Pd-IPr. The bis-aminated pre-catalyst Pd-PEPPSI-IPr(NMe2)2 was shown to be the most active and stable pre-catalyst, and it was shown to be also highly efficient in more challenging amination reaction. It indeed allows to carry out the amination of aryl chlorides at low catalyst loadings or by using a mild base such as cesium carbonate, and even to activate the aryl tosylates, which are more difficult substrates than aryl chlorides. In order to study the critical stereoelectronic properties of the NHC ligands for the efficiency of the corresponding catalysts, further derivatization of the heterocyclic backbone was carried out, either by increasing the bulkiness of the mono-amino group from dimethylamino to diisopropylamino group to generate the carbene IArNiPr2, or by formally replacing one dimethylamino group by an halogen X in the bis-aminoimidazo-2-ylidene to give the carbenes IArNMe2,X. While the imidazolium salts (IArNiPr2)·HOTf was synthesized following the same method as (IArNMe2)·HOTf, the oxidative halogenation of the backbone of (IArNMe2)·HOTf with a N-halosuccinimide afforded (IArNMe2,X)·HOTf in good yields under very mild conditions. Noteworthy, this original reactivity was also observed on the rhodium and palladium complexes of this ligand.

The synthesis and characterization of a series of chiral indium complexes bearing a tridentate NNO ligand are reported. The ligand 2-[[[(dimethylamino)cyclohexyl]amino]methyl]- 4,6-bis(tert-butyl) phenol (H₂NNO) was synthesized via a previously published procedure and bound to indium by both a protonolysis and salt metathesis route. A dimethylated indium complex (NNO)InMe₂ (1) was isolated by reaction of InMe₃ with H₂NNO. A one-pot saltmetathesis route was used to produce a unique mixed-bridge dinuclear indium complex [(NNO)InCl] ₂(μ-OEt)(μ-Cl) (3) from a mixture of indium trichloride, potassium ethoxide and the monopotassiated salt of the ligand, KH(NNO). Direct reaction of KH(NNO) and indium trichloride resulted in the formation of (NNO)InCl₂ (4) which was carried forward to 3 by reaction with sodium ethoxide. The complex 3 is active for the ROP of β-butyrolactone ε-caprolactone and lactide and is the first reported indium-based catalyst for lactide or β-butyrolactone ROP. Kinetic studies of 3 for ROP of LA revealed that catalyst was well-behaved, and that the rate was first order with regard to lactide and catalyst. The enthalpy and entropy of activation for the ROP were experimentally determined. Polymer produced by ROP by 3 has narrow molecular weight distribution and a good correlation is seen between the observed moleular weight and monomer loading. A mechanism was proposed for 3 acting as a catalyst for the ROP of lactide; however further experiments are required to confirm this mechanism. Polymer samples isolated from the ROP of rac-lactide by rac-3 show isotactic enrichment. It is postulated that the chiral catalyst 3 is exerting stereocontrol via an enantiomorphic site control mechanism. / Science, Faculty of / Chemistry, Department of / Graduate

Les travaux présentés dans ce manuscrit ont trait à la catalyse de polymérisation des α-oléfines sont présentés en 4 parties distinctes. La première est consacrée à l'étude d'un système catalytique pour la production de polypropylène élastomère. L'analyse poussée des polymères produits et la caractérisation complète des catalyseurs utilisés a permis de montrer la présence de deux homopolymères sous forme de blende. La seconde partie porte sur la copolymérisation de monomères bifonctionnels vinyl-vinylidène avec le propylène. La caractérisation des polymères a permis de révéler la réactivité particulière des liaisons vinylidène et d'étudier l'influence du catalyseur utilisé sur le mécanisme de la polymérisation. La troisième partie s'intéresse à la caractérisation des espèces active en polymérisation et à l'étude des mécanismes d'activation et de désactivation des catalyseurs métallocènes. La synthèse et la caractérisation d'espèces cationiques, l'étude de leur comportement dynamique en solution, ainsi que l'évaluation de leur productivité en polymérisation ont permis d'établir un lien entre les propriétés électrophiles de ces espèces et de leur activité en polymérisation. La dernière partie porte sur l'homopolymérisation d'α-oléfines encombrées. La recherche d'un catalyseur suffisamment productif nous a amené à tester plusieurs catalyseurs présentant des structures différentes. L'absence de catalyseur productif soulève l'hypothèse d'interactions désactivantes entre le catalyseur et le monomère. / The work presented in the manuscript focus on α-olefin polymerization catalysis, and is divided into four distinct parts. The first part is dedicated to the study of catalytic systems for the production of elastomeric polypropylene. The analysis of the produced polymers and the characterization of the catalysts showed the presence of two homopolymers as a blend in the elastomeric polypropylene. The second part focuses on the copolymerization of bifunctionnal vinyl-vinylidene monomers with propylene. The characterization of the polymers revealed the reactivity of the vinylidène bonds and showed different polymerization mechanisms for the different catalysts. The third part reports a study on the activation and deactivation pathways of the active species in polymerization. The characterization of model cationic species and the study of their behavior in solution and in polymerization showed the relationship between the electrophilicity of the species and its productivity in propylene polymerization. The last part is dedicated to the polymerization of hindered α-olefins. The quest for a productive catalyst led to test various single site catalysts with different structures. Deactivating interactions between the monomers and the catalyst are supposed to explain the low productivity of the tested catalysts.

On choisit un groupe algébrique G, un sous-groupe algébrique H de G ; on choisit une mesure de probabilité borélienne μ sur G. On considère alors la chaîne de Markov sur l’espace homogène X = G/H de probabilité de transition Px = μ * δx pour x ε X. Dans cette thèse, on étudie les propriétés de récurrence de ces marches aléatoires.On s’intéresse à deux types de récurrence : la récurrence presque-sûre (toute trajectoire revient presque-sûrement infiniment souvent dans un compact) et la récurrence en loi (il existe une mesure de probabilité μ stationnaire sur X .On s’intéresse également aux éventuelles propriétés de transience presque-sûre (toute trajectoire quitte presque-sûrement définitivement tout compact).On construira d’abord un exemple où on n’a ni récurrence presque-sûre en tout point, ni transience presque-sûre en tout point. On montrera ensuite un critère de récurrence presque-sûre dans le cas où G est un groupe de Lie semi-simple ; on a en fait dans ce cas une dichotomie : soit tous les points sont récurrents,soit tous les points sont transients.Dans le cas où G est le groupe affine GL(d,ℝ) α ℝd,on donnera un critère de récurrence en loi sur les Grassmanniennes affines, et, dans un dernier chapitre, on donnera quelques résultats partiels d'un projet en cours,permettant de donner des résultats pour le groupe SO(p, p+1) α ℝ2p+1. / Choose an algebraic group G, and an algebraic subgroup H. Choose a Borel probability measure μ on G. Consider the Markov chain on the G-space X = G/H with transition probability Px = μ * δx for x ε X.The point of this dissertation is the study of the recurrence properties of such a random walk.We consider two types of recurrence : almost-certain recurrence (i.e. almost-every trajectory enters some compact set infinitely often) and the associated almost-certain transience (where almost-every trajectory eventually leaves every compact set) and recurrence in law (i.e. there exists a μ stationary probability measure on X).First, we show that, in general, there is no dichotomy between almost-certain recurrence and transience by constructing an example with both almost-certainly recurrent and almost-certainly transient points.We then prove a criterion for almost-certain recurrence when G is a semi-simple Lie group and X is a G-space. In fact, in this case, we have a dichotomy where either every point of X is almost-certainly recurrent, or every point of X is almost certainly transient.When G is the affine group GL(d,ℝ) α ℝd, we give a criterion for recurrence in law on the affine Grassmannians.In the final chapter, we give some partial results from an ongoing project,which give a criterion for recurrence in law the group SO(p,p+1)α ℝ2p+1.

Les allènes ont longtemps été perçus comme des curiosités scientifiques notamment à cause de leur réactivité et de leur structure très particulières. Cependant ils bénéficient d'une attention de plus en plus importante de la part des chercheurs depuis plusieurs décennies grâce au développement de méthodes efficaces pour les synthétiser. Au cours de cette thèse, nous nous sommes intéressés à l'hydrofonctionnalisation intermoléculaire de ces molécules insaturées. Les hydrofonctionnalisations sont généralement des réactions très efficaces, qui permettent d'éviter la production de déchets, et qui donnent accès à un très large panel de produits d'intérêts. Jusqu'à maintenant, les réactions d'hydrofonctionnalisations d'allènes ont nécessité l'emploi de systèmes catalytiques faisant appel à des métaux précieux combinés à des ligands complexes. Notre objectif était de rendre ces réactions réalisables avec le système le plus simple possible et un catalyseur peu onéreux et peu toxique : le cuivre. Nous avons tout d'abord étudié les réactions d'hydroaminations, qui ont été réalisées avec de nombreux allènes variés. Par la suite, nous avons souhaité démontrer le potentiel de notre système catalytique, en étendant cette réactivité pour la création de liaisons C-C et C-O. / Allenes were perceived as scientific oddity for a long time, due to their particular reactivity. But they are currently attracting a growing interets of chemists since the discovery of efficient synthesis for these compounds in the past few decades. During this thesis, we focused on intermolecular hydrofunctionalization of these substrates. Hydrofunctionalization process generally avoid the production of any wastes, and give an efficient access to a large scope of valuables compounds. Until now, allenes hydrofunctionalizations required the use of catalytic systems using precious metals combined with complex ligands. Our goal was to perform this sort of reaction with a simplest possible system using a cheap metal with low-toxicity : copper. We started studying hydroaminations process, which were realized on a large scope of allenes. Subsequently, we wanted to demonstrate the potential of our new catalytic system and so applied it for the creation of C-C and C-O bonds.

Orientador: Sergio Augusto Mello da Silva / Resumo: Estudos sobre florestas plantadas para aproveitamento de madeiras em vários setores industriais tem se intensificado no mundo. A utilização dessas madeiras no Brasil, além de garantir a sustentabilidade de espécies nativas, possibilita a produção de derivados de madeiras e o amplo emprego na construção civil. A Seringueira (Hevea brasilienses) e Teca (Tectona grandis) representam duas espécies de reflorestamento cultivadas no Brasil e que serão utilizadas neste trabalho para produção de painéis de partículas homogêneas. A Seringueira é utilizada para produção de borracha natural, entretanto, precisam ser substituídas ao final do ciclo de produção (25 a 30 anos) e, as árvores improdutivas são utilizadas para geração de energia. Com relação à Teca, espécie de origem asiática, sua madeira apresenta excelentes características de resistência e durabilidade e vem sendo empregada na construção civil de modo geral e para a produção de móveis. Vale ressaltar, que tanto a Seringueira quanto a Teca, adaptadas às condições edafológicas das regiões em que são reflorestadas, apresentam rápido crescimento e poderiam ser utilizadas para produção de painéis de partículas. Entretanto, para este trabalho, será considerada a utilização dessas espécies com mais de 20 anos, buscando-se avaliar a possibilidade de aproveitamento dessas para a produção de painéis de partículas aglutinadas com adesivo poliuretano derivado de mamona (PU-Mamona). Os painéis produzidos foram avaliados de acordo com NBR 1... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Studies on planted forests to use wood in various industrial sectors has intensified in the world. The use of these woods in Brazil, in addition to ensuring the sustainability of native species, enables the production of wood derivatives and wide employment in civil construction. The rubber tree (Hevea brasilienses) and Teca (Tectona grandis) represent two species of reforestation cultivated in Brazil and which are used in this work for the production of particleboards. The rubber tree is used for the production of natural rubber, however, it needs to be replaced at the end of the production cycle (25 to 30 years) and, the unproductive trees are used for power generation. Regarding Teca, a species of Asian origin, its wood has excellent resources of resistance and durability and has been used in civil construction in general and for furniture production. It is worth mentioning that both Seringueira and Teca, adapted to the edaphological conditions of the regions where they are reforested, show quick growth and are used for the production of particleboards. However, for this work, the use of these species with more than 20 years will be considered, looking for the possibility of using them for the production of agglutination panels with castor oil-based polyurethane adhesive (PU-Castor). The panels produced were evaluated according to NBR 14810 - 1 and 2: 2013 and international documents to verify their physical and mechanical properties, as well as, using scanning electron mi... (Complete abstract click electronic access below) / Mestre

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21571号 / 理博第4478号 / 新制||理||1642(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)准教授 菅沼 秀夫, 教授 永江 知文, 教授 田中 貴浩 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Vapor generation is central to the flow dynamics within fuel injector nozzles. Because the degree of atomization affects engine emissions and spray characteristics, quantification of phase change within diesel fuel injectors is a topic of design interest. Within the nozzle, the large pressure gradient between the upstream and downstream plena induce large velocities, creating separation and further pressure drop at the inlet corner. When local pressure in the throat drops below the fluid vapor pressure, phase change can occur with sufficient time. At the elevated temperatures present in diesel engines, this process can be dependent upon the degree of superheat, motivating the modeling of heat transfer from the wall. By modeling cavitation and flash boiling phenomena as a departure from equilibrium conditions, the HRMFoam model accurately reproduces canonical adiabatic flows. An experimentally determined relaxation time controls the rate at which vapor is generated, and includes model constants tuned for water and a diesel fuel surrogate. The model is shown to perform well for several benchmark experimental cases, including the work of Reitz, Lichtarowicz, and Nurick. With the implementation of the Farve-averaged energy equation, the present work examines and validates the transport of enthalpy through the fixed heat flux and fixed wall temperature boundary conditions. The pipe heat transfer experiments of Boelter and Allen are replicated using the kEpsilon, Realizable kEpsilon, and Spalart-Allmaras models. With proper turbulence model selection, Allen's heat transfer coefficient data is reproduced within 2.9%. Best-case bulk temperature rise prediction is within 0.05%. Boelter's bulk temperature rise is reproduced within 16.7%. Turbulent diffusivity is shown to determine radial enthalpy distribution.

京都大学 / 新制・課程博士 / 博士(情報学) / 甲第23546号 / 情博第776号 / 新制||情||132(附属図書館) / 京都大学大学院情報学研究科数理工学専攻 / (主査)教授 山下 信雄, 教授 太田 快人, 教授 永持 仁 / 学位規則第4条第1項該当 / Doctor of Informatics / Kyoto University / DFAM