Domino catalysis is an ideal strategy in the synthesis of heterocyclic scaffolds, as multiple bonds can be formed under a single set of reaction conditions. In this work, we present the development of two novel domino processes which afford access to aza-analogues of the dihydrodibenzoxepine motif. Careful optimisation revealed that the Rh catalysed hydroarylation proceeds under mild conditions as compared to the C-O coupling. Furthermore, Pd was not required for the C-O bond formation when using alkenyl pyrazines as substrates. Variation of the substituents on both the heterocycle and on the boronic ester provided insight into the structural features required for successful domino reaction, and a stepwise protocol was developed for incompatible substrates. We have also developed the first multi-metal, multi-ligand domino reaction featuring both a chiral and achiral ligand in the same pot, still leading to an enantioenriched product.

The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl2bpy)2(OH2)2](Z)2 (2, Z = CF3SO3; 3, Z = (3,5-(CF3)2C6H3)4B ,i.e. BArF), cis-[Ru(4,4′-Cl2bpy)2(OH2)2](Z)2 (4, Z = CF3SO3; 5, Z = BArF) and cis-[Ru(bpy)2(PR3)(OH2)](CF3SO3)2 (7, bpy = 2,2’-bipyridine, PR3 = P(C6H4F)3; 8, bpy = 2,2-bipyridine, PR3 = PPh3; 9, bpy = 4,4’-dichloro-2,2’-bipyridine, PR3 = PPh3; 10, bpy = 4,4’-dimethyl-2,2’-bipyridine, PR3 = P(C6H4F)3) for the hydrogenation and hydrogenolysis of furfural (FFR), furfuryl alcohol (FFA) and 5-hydroxymethylfurfural (HMF) was investigated. The compounds 2-5 are active and highly selective catalysts for the hydrogenation of FFR to FFA. Using 2 as catalyst at 100 °C, hydrogenation of FFR proceeded to high conversion (≥98%) and with 100% selectivity to FFA in 2 h. The catalyst cis-[Ru(6,6′-Cl2bpy)2(OH2)2](CF3SO3)2 (2) also showed some activity for hydrogenolysis of FFR and FFA at 130 °C in ethanol, giving up to 25% of 2-methylfuran (MF) yield. The catalyst 3 alsodisplayed high catalytic activity for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Catalysts 7-10 are also active towards the hydrogenation of furfural (FFR) in NMP giving >90% FFR conversion with 100% selectivity for furfuryl alcohol (FFA) in 12 h. Compounds 7-10 are active C-O bond hydrogenolysis catalysts in presence of bismuth halide Lewis acids. For example, hydrogenolysis of FFA in the presence of 1 mol% of catalyst cis-[Ru(4,4’-Cl2bpy)2(PPh3)(OH2)](CF3SO3)2 (9) and 20 mol% bismuth bromide at 180 °C/51 atm H2 pressure gave >96% conversion of FFA and 55% MF yield. Compounds 7-10 in the presence of bismuth halides, showed almost 100% conversion of HMF with a very high selectivity (65-72%) for 2,5-DMF, along with 10-12% of MF, and trace amount of 5-methylfurfural (MeFFR). In order to test the activity of ruthenium hydrides towards the C-O bond hydrogenation and hydrogenolysis of HMF, series of monocationic ruthenium complexes cis-[Ru(bpy)2(PR3)(H)](CF3SO3) (12, bpy = 2,2’-bipyridine, PR3 = P(C6H4F)3; 13, bpy = 2,2-bipyridine, PR3= PPh3; 14, bpy = 4,4’-dimethyl-2,2’-bipyridine, PR3= P(C6H4F)3) were prepared. The hydrogenation of HMF using catalysts 12-14, produced 70-72% of 2,5-DMF and 11% MF, suggesting that ruthenium hydrides are active and efficient catalysts for HMF hydrogenation.

Hicks Dome is a mineralized intrusive center of alkaline ultramafic dikes, plugs and diatreme breccias that produced ~1200 m of structural doming of Paleozoic sedimentary rocks in southeastern Illinois. It is part of an igneous province referred to as the "Wauboukigou Alnöite Province" or "Middle Mississippi Alkaline Province". The 40Ar/39Ar dating of biotite and hornblende from igneous rocks throughout the region has consistently produced crystallization ages of 270 +/- 2 Ma (Early-Middle Permian). Hicks Dome lies near the intersection of two aulacogens, the Reelfoot Rift and the Rough Creek Graben. The igneous rocks in the Hicks Dome area range from dark-green, porphyritic dikes, through dikes with pelletal lapilli, to carbonate cemented breccias with country rock fragments and, locally, phenocrysts or xenocrysts and pelletal lapilli. Magmatic minerals include diopside, pargasite, phlogopite-biotite, titanomagnetite, ilmenite, and apatite, as well as carbonate (ferroan-dolomite - ankerite and calcite) of possible magmatic origin. This mineral assemblage only partly corresponds with other occurrences in the middle Mississippi Valley region igneous province as melilite, garnet, olivine, and perovskite were not identified in the Hicks Dome samples. The Hicks Dome igneous lithotype is defined here as a minette, a type of calc-alkaline lamprophyre. Evidence for this classification includes abundant Al-rich phlogopite-biotite, diopside, and pargasite, and the absence of melilite, garnet, and perovskite. Additionally, plotted Al2O3 vs. TiO2 compositions of biotite-phlogopite form a trend subparallel to that of minettes and alnöites, and Al vs. Ti values for most clinopyroxenes fall in the minette field. Some other igneous occurrences in the region are classified as types of ultramafic lamprophyres. For example, the North Hutson mine (Kentucky) and the Cottage Grove (Illinois) dikes are identified as alnöites and the Wildcat Hills dike (Illinois) is regarded as an aillikite. The Hicks Dome igneous suite contains 23 - 25 wt. % SiO2 and 13 - 21 wt. % CO2, whereas regional igneous rocks contain 33 - 36 wt. % SiO2 and 1 - 2 wt. % CO2. Such high CO2 values and inferred carbonate abundance is likely related to the elevated REE values at Hicks Dome. Finally, Hicks Dome samples show relative depletions in Ti, Nb, Ta, Zr, and Hf on a spider diagram compared to other regional igneous occurrences. These data indicate more variability among provincial igneous rocks than previously realized and perhaps two types of lamprophyres, one a calc-alkaline such as at Hicks Dome, and the other an alkaline ultramafic type. Rock samples from Hicks Dome and the surrounding region that were analyzed far exceed the silica cut-off to be considered a carbonatite (sensu stricto), yet a strong, consistent spatial association of abundant carbonate with igneous rocks throughout the region and similar patterns in LIL (large ion lithophyle), HFS (high field strength) and RE (rare earth) elements with carbonatites worldwide supports that magmatic carbon was part of the lamprophyre system at Hicks Dome. Carbon and oxygen isotope values for carbonate from Hicks Dome and other regional igneous samples do not plot within the field for primary carbonatite or the field for unaltered Mississippian limestone and instead form a broad linear trend between these two reference fields. The observed isotopic trend was possibly due to alteration of primary carbonatite by magmatic-hydrothermal and later low-temperature connate fluids. Parisite and/or synchysite, two REE fluorocarbonates of the bastnäsite group, and xenotime, a Y-(REE) phosphate, were identified in the Hicks Dome samples and occur as fibroradial aggregates in dissolution cavities in fluorite and carbonate and as anhedral crystals infilling microfractures and cleavage planes of phlogopite-biotite and paragasite. These textures clearly indicate the REE minerals are secondary phases most likely resulting from hydrothermal alteration-replacement by magmatic-hydrothermal fluids. A fertile (LREE enriched) lithospheric metasomatized mantle likely sourced the Hicks Dome carbonated alkaline silicate magma that, during emplacement, domed and brecciated the Paleozoic strata, expelled magmatic-hydrothermal fluids, and generated a F-REE mineralizing fluid with abundant carbonate. Igneous activity at Hicks Dome is genetically related to F-REE-base metal mineralization hosted by diatreme breccias, and likely contributed fluorine to the connate brines responsible for the F-base metal mineralization of the surrounding Illinois-Kentucky Fluorspar District (IKFD). Although resource estimates for the Hicks Dome area are beyond the scope of this work, an economic deposit of F, REEs, and/or base metals may be present at Hicks Dome and other igneous occurrences. The igneous lithotype, mineralogy, whole rock geochemistry, and regional geologic context support such a conclusion.

This thesis is centred around sequential C-C bond forming processes using oxygenated electrophiles. A major part of this research focuses on the constructive deoxygenation of 2-methoxyphenol (guaiacol), a major breakdown product of the renewable feedstock, lignin. 1,2-dielectrophiles are known to be challenging substrates for catalysis if both leaving groups are of similar reactivity, however high selectivity was observed in the palladium- catalysed Grignard cross-coupling of 2-methoxyphenyl-1H-imidazole-1-sulfonate. The previously untested Grignard cross-coupling catalyst, [PdCl₂(Xylyl-Phanephos)], was found to be highly active. A 2-benzoxazolyl functionality was shown to be an excellent directing group for the chelation-controlled nucleophilic aromatic substitution of aryl methyl ethers. However, this modified Meyers reaction is limited to aryl ethers containing an ortho-chelating group. To expand the ether scope, nickel-catalysed Grignard cross-coupling was studied. [NiCl₂(PⁿBu₃)2] showed increased activity in the Grignard cross-coupling of challenging ortho-substituted anisoles compared to the well-renowned [NiCl₂(PCy₃)2] and several Ni0 -NHC systems, with a ligand steric effect demonstrated. The success of [NiCl₂(PⁿBu₃)2] was extended to more activated methoxynaphthalene substrates, in which the lowest reported catalyst loadings (0.1-0.25 mol%) were reported. Induction periods at 0.1 mol% suggested the requirement of inorganic Lewis-acidic magnesium salts to be formed in situ before any considerable activity was observed. Further work is required to increase reaction and ether scope, but this work provides a basis for exploiting lignin- derived phenols as a framework in the synthesis of functionalised chemicals of higher value. The final results chapter concerns an alternative sequential C-C bond forming process using another oxygenated electrophile. [PdCl₂((S)-Xylyl-Phanephos)] was used to accomplish a Grignard cross-coupling of vinyl tosylate, with the product then subjected to a highly enantioselective methoxycarbonylation using the same catalyst. This lead to a concise synthesis of (S)-Flurbiprofen.

Logging of cores of the Upper Permian and Lower Triassic Khuff Formation, Ghawar, Saudi Arabia, has allowed a high resolution sequence stratigraphic framework to be generated. The lithofacies of this huge, arid epeiric ramp succession include: subaqueous -and supratidal anhydrite, tidal flat laminites, lagoonal mudstone, ooid-peloid grainstone, and subtidal off-shoal open marine mudstone. Third order sequences include the Late Permian upper Khuff C, the Early Triassic Khuff B and the Khuff A sequences, which corrrelate with global cycles. Seven high frequency sequences (HFSs) make up the Changhsingian upper Khuff C. These HFSs are ~400 k.y. duration and probably driven by long term eccentricity. The Early Triassic Khuff B and A sequences are made up of 4 HFSs each, which appear to be ~100 to 200 k.y. duration and not easily tied to eccentricity forcing. The HFSs are in turn composed of parasequences, which appear to be 10 to 20 k.y. average durations, suggesting precessional and half precessional forcing. However, many thin locally developed cycles may be autocycles or subprecessional cycles. Sequence stratigraphic cross sections and facies maps document progradation directions on the platform, reflecting the subtle interplay between the Ghawar structure and regional paleoslopes. Anhydrites are rare in the Permian Upper Khuff C except near the base of the studied interval. Anhydrites are well developed in the Triassic Khuff B and Khuff A where some form transgressive deposits while others are highstand deposits of high frequency sequences. The Permian-Triassic boundary (PTB) on the Arabian Platform marks a significant relative sea-level drop, that exposed from the outcrop belt to somewhere east of Ghawar. This contrasts with transgressive PTB settings elsewhere. Across the PTB the mass extinction is marked by a major decrease in biotic groups. The extinction was followed by development of subtidal thrombolites and increased microbial calcification due to decreased bioskeletonization. The dominant reservoirs in the Permian Upper Khuff C occur in oolite in the uppermost high frequency sequence. In the Triassic Khuff B and A the reservoir facies are commonly non-dolomitized oolitic facies associated with open lagoon carbonates distant from evaporitic tidal flats. Within dolomitized units, best reservoirs are associated with oomoldic porosity, but oolite units proximal to evaporitic tidal flats have porosity plugged by anhydrite. Carbon and oxgyen isotope profiles up to 150 m long were obtained from cored wells of the Khuff Formation, Ghawar Field, Saudi Arabia, across the Permian-Triassic boundary. Major global excursions are at the Changhsingian-Wuchiapingian boundary and the Permian-Triassic boundary, but several smaller excursions also appear to correlate with excursions elsewhere. The presence of the negative C-isotope excursions globally in both δ¹³Ccarbonate and δ¹³C organic as well as in deeper water sections lacking emergence surfaces, strongly supports the idea of these excursions being global phenomena related global C cycling. Over 75% of the negative carbon isotope excursions in Ghawar occur beneath emergence surfaces, including the two major excursions at the Wuchiapingian and Changhsingian stage boundaries. The δ¹³C profiles beneath the boundaries resemble those iii associated with early diagenesis associated with isotopically light soil gas. The δ¹⁸O profiles beneath the surfaces are variable, perhaps reflecting variable effects of evaporation on the meteoric input, mixing or overprinting by burial diagenesis. This suggests that the C-isotope excursions on the Arabian Platform, although global in origin, appear to have been modified by early diagenesis. U depletion across the boundary is compatible with the postulated origins of the PTB event with bottom waters becoming stagnant and reducing, as a result of warming induced by volcanogenic CO₂ released by Siberian trap volcanism, methane release from thermal metamorphism of coals and destabilization of clathrates in the deep sea due to ocean warming. The global extent of the C-isotope and U excursions provides a high resolution correlation tool for Late Permian and Early Triassic successions. / Ph. D.

La conception de ligands est d'une grande importance pour le développement de la catalyse métallique, conformément à une approche de chimie durable.La première partie de cette thèse porte sur une revue bibliographique détaillée des ligands phosphorés couramment employés dans les systèmes catalytiques pour les réactions de couplage carbone‒carbone catalysées au palladium. La deuxième partie traite du contrôle conformationnel du squelette ferrocénique dans les ligands polyphosphines. Ce contrôle conformationnel vise à induire des interactions inédites entre deux atomes de phosphore, et également avec des centres métalliques. De nouveaux anions cyclopentadiényles substitués et encombrés ont été synthétisés, et ont permis de réaliser la synthèse de triphosphines ferrocéniques inédites. Les réactions avec le fer (II) des sels d'anions cyclopentadiényles substitués par des groupements encombrés (tertio-butyle, trityle, super-trityle) et des groupements phosphino enrichis ou appauvris en électrons (isopropyle, cyclohexyle, furyle) ont conduit à une série de nouveaux ligands polyphosphines ferrocéniques multidentes. Leurs coordinations à des sels de palladium ou de platine ont été étudiées. Les complexes de coordination correspondants ont été isolés avec de très bons rendements et caractérisés en solution par RMN 1H, 13C, 31P et à l'état solide par Diffraction des Rayons X.La troisième partie décrit la synthèse et la caractérisation de diphosphines ferrocéniques inédites. Des investigations ont été menées en électrochimie sur ces ligands et les propriétés électroniques des dérivés séléniés correspondants ont été étudiées par RMN 31P‒77Se.Ces ligands se sont montrés des auxiliaires efficaces pour l’arylation pallado-catalysée d’hétéroaromatiques dans l’activation C‒H ou dans le couplage C‒O, surtout à faible charge de catalyseur, en accord avec les exigences du développement de chimie durable / The design of ligands is of great importance for the development of metal catalysis, in keeping with an ever more sustainable approach of chemistry.The first part of this thesis focuses on a detailed literature review of phosphorus ligands commonly used in catalytic systems for the coupling reactions catalyzed carbon-carbon palladium.The second part deals with the conformational control of the ferrocene backbone within polyphosphine ligands. This conformational control aims at inducing unedited interactions between phosphorus atoms, and also with metal centers. New substituted and hindered cyclopentadienyl rings were synthesized, which allow the assembling of original ferrocenyl triphosphines. The reactions with iron(II) salts of cyclopentadienyl anions substituted with hindering groups (tert-butyl, trityl, super-trityl) and holding either electron-donor or electron-withdrawing phoshino groups (isopropyl, cyclohexyl, furyl) afford a set of novel multidentate ferrocenyl phosphine ligands. Their coordinations towards palladium and platinum were studied. The corresponding coordination complexes were isolated in high yields and fully characterized in solution by multinuclear 1H, 13C, 31P NMR and in solid state by X-Ray cristallography.The third part describes the synthesis and characterization of original ferrocenyl diphosphines. Electrochemical investigation of these ligands and electronic properties of their corresponding diselenide derivatives by NMR 31P‒77Se coupling constants were studied.These ligands were found efficient auxiliaries for palladium-catalyzed arylation of heteoaromatics through C–H bond activation or C‒O coupling, especially at low loading of catalyst, in agreement with sustainable chemistry development requirement

Les réactions de macrocyclisation constituent un défi pour les chimistes de synthèse, car les sélectivités pour les réactions intramoléculaires par rapport à celles intermoléculaires sont difficiles à maximiser. Celles-ci sont donc effectuées dans des milieux dilués et sont souvent lentes. La chimie en flux continu a été utilisée pour améliorer les réactions présentées dans cette thèse, car elle permet un meilleur transfert de masse qui se traduit par un mélange et un chauffage plus efficace, donc des temps de réaction plus courts. À la suite d’introductions sur les macrocycles (Chapitre 1) et sur la métathèse d’alcènes (Chapitre 2), nos efforts pour améliorer l’étape de macrocyclisation par métathèse d’alcènes d’un musc découvert par l’industrie des fragrances sont décrits au chapitre 3. Alors que les conditions rapportées ne permettaient pas de réaliser cette réaction de façon reproductible sur une échelle de plus de 100 mg, il a été possible de l’effectuer sur une échelle d’un gramme grâce à l’emploi du catalyseur approprié. La réaction a été effectuée dans un montage traditionnel (ballon à fond rond) à température ambiante pour fournir 57% du macrocycle désiré après 5 jours. En comparaison, le montage en flux continu n’a nécessité que 5 minutes de temps de résidence à 150 °C pour fournir 32% de rendement. Le second projet présenté dans cette thèse porte sur la synthèse totale de la néomarchantine A (Chapitre 5) et est précédé d’une introduction sur les composés bisbibenzyliques (Chapitre 4). Cette synthèse a permis de démontrer l’avantage d’incorporer plusieurs étapes clés en flux continu. Différentes conditions ont été investiguées pour réaliser les deux étapes de couplage C-O en début de synthèse. Les meilleurs résultats ont été obtenus avec le couplage de Chan-Evans-Lam dans un cas (34%) et la substitution nucléophile (SNAr) dans l’autre (71%), ce qui a permis de s’éloigner des conditions classiques de couplage d’Ullmann. La première macrocyclisation par métathèse d’alcènes pour la synthèse d’un composé bisbibenzylique est également rapportée. Les conditions en flux continu ont permis de réaliser la réaction en seulement 10 minutes de temps de résidence avec un rendement de 49%, ce qui est similaire au rendement obtenu dans un montage traditionnel, mais qui nécessite 17 heures de temps de réaction. Précédé d’une introduction sur la photochimie (Chapitre 6), le chapitre 7 décrit la conception et l’évaluation d’un réacteur en flux continu adapté à la macrocyclisation photochimique. Celui-ci est inspiré des réacteurs à agitation continue (CSTR), mais est aminci pour permettre une irradiation plus uniforme. Son efficacité a été démontrée par l’application de la réaction d’oxydation aérobique de thiols en disulfures. En plaçant plusieurs réacteurs en série, un rendement d’environ 47% a été obtenu peu importe l’échelle de la réaction, allant de 100 mg à 1 g. En comparaison, le montage traditionnel, le réacteur standard en flux continu (PFR) ainsi que le réacteur CSTR n’ont pas été en mesure de fournir plus de 20% du macrocycle désiré. L’étendue de la réaction a été démontrée en synthétisant différents macrocycles d’intérêt biologique ou structurel avec des rendements entre 33 % et 50 %. / Macrocyclization reactions pose a challenge for synthetic chemists because the selectivity for the intramolecular reaction over intermolecular is difficult to achieve. They are usually done in diluted medium and are often slow. Continuous flow chemistry has been used to improve the reactions developed in the present thesis by allowing better mass and energy transfer which results in more efficient mixing and heating, and thus shorter reaction times. Following introductions on macrocycles (Chapter 1) and olefin metathesis (Chapter 2), our efforts to improve the olefin metathesis macrocyclization step of a musk discovered by the fragrance industry are described in Chapter 3. While the reported conditions did not allow the reaction to be performed reproducibly on a scale greater than 100 mg, the use of the appropriate catalyst allowed us to perform the reaction on a gram scale. The reaction was carried out in batch at room temperature to provide 57% of the desired macrocycle after 5 days. In comparison, the continuous flow setup required only 5 minutes of residence time at 150 °C to provide 32% yield. The second project focuses on the total synthesis of neomarchantine A (Chapter 5) and is preceded by an introduction on bisbibenzyl compounds (Chapter 4). The goal of the synthesis was to show the advantage of integrating several key steps in continuous flow. Different conditions were investigated to carry out the two C-O bond forming steps early in the synthesis. The best results were obtained with Chan-Evans-Lam coupling in one case (34%) and a SNAr reaction in the other (71%), which allowed to deviate from the classical conditions of Ullmann coupling. The first macrocyclization by ring-closing metathesis for the synthesis of a bisbibenzyl is also reported. The continuous flow conditions produced a 49% yield of a key macrocycle, which is similar to the batch results but only required 10 minutes of residence time in flow instead of 17 hours of reaction time in batch. Preceded by an introduction on photochemistry (Chapter 6), Chapter 7 describes the design and evaluation of a continuous flow reactor suitable for photochemical macrocyclization. It is inspired by CSTR reactors but is “flattened” to allow a uniform irradiation. Its effectiveness has been demonstrated by the application of aerobic oxidation of thiols to disulfides. By placing reactors in series, a yield of 47% was obtained regardless of the scale, ranging from 100 mg to 1 g. In comparison, the batch setup as well as the CSTR and PFR reactors were not able to provide more than 20% of the desired macrocycle. The scope of the reaction was demonstrated by synthesizing different macrocycles of biological or structural interest in yields of 33-50%.

No description available.

Made available in DSpace on 2014-12-17T15:37:23Z (GMT). No. of bitstreams: 1 VivianeSM.pdf: 285646 bytes, checksum: 806d8cb57146ca69bbc7d647f187939d (MD5) Previous issue date: 2007-05-07 / The stress responses can be parameters used in order to identify the welfare of animals. Behavior parameters can also be regarded as means to identify their relation to stressing situations. In this study, adult male and female poodle dogs, accustomed (group 1) or not (group 2) to the environment of a bath and grooming salon were analyzed through the plasmatic concentration of cortisol, cell counting of the immune system (total leukocytes and percentage of neutrophils and lymphocytes) and through observation of changes in behavior before and after the bath and grooming service. After arriving at the kennel, the dogs were taken to the bath and grooming facility, where they had their blood samples taken and were observed for ten minutes. The subsequent procedures consisted of the bath and grooming services and the collection of another blood samples. The research results were analyzed through non-parametric statistic tests and p < 0.05. Accustomed and non-accustomed dogs presented different hormonal and behavior responses: accustomed dogs presented an increasing of the cortisol level at the second blood samples collection, thus indicating stress towards the aforementioned procedures and presenting behavior responses which can be described as moderated stress. Non-accustomed dogs presented the same cortisol levels in both first and second samples suggesting that they were already reacting to the new environment. Dogs also shown behavioral responses which can be described as acute stress. Both male and female dogs showed similar immunological changes as well as different endocrine and behavioral profiles. Concerning aggression, this study demonstrates that biting the owner can be a predicting behavior of aggression during the bath and grooming service, male dogs were more aggressive than the female, and that males were more reactive to unknown caretaker. The results of this research propose that the familiarization of the animal with the bath and grooming environment and caretaker is important to the welfare of poodle dogs, especially to that of male dogs / As respostas de estresse podem ser vari?veis utilizadas para identificar o n?vel de bem-estar dos animais. Par?metros comportamentais tamb?m podem ser usados tentando identificar sua correspond?ncia com situa??es estressantes. Neste estudo c?es da ra?a poodle, adultos, de ambos os sexos, familiarizados (Grupo 1) e n?o familiarizados (Grupo 2) a um ambiente de sal?o de beleza canino foram avaliados por meio da concentra??o plasm?tica de cortisol, contagem de c?lulas do sistema imune (leuc?citos totais e percentuais de neutr?filos e linf?citos) e observa??o de altera??es comportamentais antes e ap?s os procedimentos de banho e tosa. Ap?s a chegada do animal no canil, dentro do ambiente de banho e tosa, foi realizada uma primeira coleta de sangue seguida por um intervalo de observa??o de 10 minutos, realiza??o dos procedimentos de banho e tosa e coleta de uma segunda amostra de sangue. Os resultados foram analisados usando testes estat?sticos n?o param?tricos e o valor de p < 0.05. C?es familiarizados e n?o familiarizados tiveram respostas hormonais e comportamentais diferentes: os c?es familiarizados apresentaram eleva??o do cortisol na segunda coleta, indicando o estresse provavelmente aos procedimentos, e respostas comportamentais que podem ser caracterizadas como estresse moderado. Os c?es n?o familiarizados ao ambiente apresentaram concentra??es semelhantes de cortisol na primeira e segunda coletas sugerindo que a situa??o estressante parece ser anterior aos procedimentos, provavelmente relacionada ao novo ambiente. Apresentaram tamb?m respostas comportamentais que podem ser caracterizadas como estresse agudo. Machos e f?meas apresentaram altera??es imunol?gicas semelhantes e altera??es end?crinas e comportamentais diferentes entre os sexos nos dois grupos experimentais. Com rela??o ? agressividade observou-se que morder o propriet?rio ? um bom preditor de agressividade durante os procedimentos de banho e tosa, os machos foram mais agressivos que as f?meas e reagiram mais a um tosador estranho. Estes resultados sugerem que a familiaridade do animal ao ambiente de tosa e banho e ao tosador ? importante para o bem-estar animal de c?es da ra?a poodle, particularmente nos machos

Made available in DSpace on 2016-04-28T20:18:30Z (GMT). No. of bitstreams: 1 2008 - Erica Mateus Toledo Accetta.pdf: 809163 bytes, checksum: 04d79d0b9854d1e99fd77cff6ae68a4f (MD5) Previous issue date: 2009-08-27 / Canine ehrlichiosis is an important infectious disease whose prevalence has been increasead in most areas of Brazil. Clinical signals and the laboratorial findings are variable. The present work had as objective to determine the frequency of the infection for E. canis and Anaplasma platys in dogs with trombocytopenia at Regi?o dos Lagos - State of Rio de Janeiro. It has been evaluated the CBC of 1127 dogs with trombocytopenia, a total of 3019 laboratorial tests carried through in the period of June 2006 and July 2007, at CEVET Lagos Lab, providing atendence to several clinics of Araruama, Iguaba Grande, S?o Pedro d Aldeia, Cabo Frio, Arraial do Cabo and B?zios. Erliquiosis was diagnosised through haemoparasit in smears of total blood s research stained with Panoptic kit. Eighty-four dogs (7.45%) were considered infected by the discovery of morulae of Ehrlichia spp. e Anaplasma platys. Normocytic normochromic anaemia and monocytosis were the most hematological alterations found. / A erliquiose canina ? uma importante doen?a infecciosa cuja preval?ncia tem aumentado significativamente em v?rias regi?es do Brasil. Os sinais cl?nicos e os achados laboratoriais s?o vari?veis. O presente trabalho teve como objetivo determinar a freq??ncia da infec??o por E. canis e A. platys em c?es com trombocitopenia na Regi?o dos Lagos do Estado do Rio de Janeiro. Foram avaliados os exames hematol?gicos de 1127 c?es com trombocitopenia de um total de 3019 exames realizados no per?odo de junho de 2006 a julho de 2007, no laborat?rio CEVET Lagos, que presta atendimento ?s diversas cl?nicas dos munic?pios de Araruama, Iguaba Grande, S?o Pedro d Aldeia, Cabo Frio, Arraial do Cabo e B?zios. A erliquiose foi diagnosticada atrav?s da pesquisa de hemoparasitos em esfrega?os de sangue total corados com kit pan?ptico. O diagn?stico baseou-se no achado de m?rulas de Ehrlichia spp. e Anaplasma platys, sendo considerados infectados 84 (7,45%) c?es. Anemia normoc?tica normocr?mica e monocitose foram as altera??es hematol?gicas mais freq?entes.