O objetivo do trabalho foi avaliar o efeito do uso de espaçadores na adaptação marginal de copings confeccionados em ligas de Ni-Cr (Verabond II) (VB II) e Ni-Cr-Be (Verabond) (VB) e Titânio cp (Tritan) (Ti-cp) fundidos pela técnica de cera perdida. A partir de uma matriz metálica, foram obtidos 135 troquéis de gesso resinado tipo IV para confecção dos padrões de cera nas seguintes condições: sem a presença de espaçador (G0), com uma camada de espaçador (G1) e com duas camadas de espaçador (G2), com quinze repetições para cada grupo. Foi realizado o enceramento de cada troquel e os padrões de cera foram incluídos em revestimento adequado para cada material. Em cada anel de fundição foram incluídos 3 padrões de cera, sendo cada um correspondente a cada condição. Cada coping, adaptado à matriz metálica por meio de um dispositivo padronizador da pressão de assentamento, foi levado ao Microscópio Óptico para aferição das medidas da desadaptação marginal. Os dados obtidos (&micro;m) foram submetidos à análise estatística (ANOVA) e teste de Tukey (p<0.05). Para a condição material, a liga VB (118,73) não apresentou diferença estatisticamente significante em relação à liga VB II (93,40), sendo que estas apresentaram diferença estatisticamente significante em relação ao Ti-cp (168,35). Em relação ao fator espaçador, houve diferença estatisticamente significante entre as três condições (G0=177,31; G1=121,51 e G2=81,66). Com base nos dados obtidos pelo presente estudo, pode-se afirmar que a presença de duas camadas de espaçador propicia menor desadaptação marginal. / The purpose of the study was to evaluate the effect of using die spacers on the marginal fit of Ni Cr (Verabond II) (VB II) and Ni-Cr-Be (Verabond) (VB) alloys and commercially pure Titanium (Tritan) (Ti-cp) casting copings by the lost wax technique. Using a metal master die, 135 Resin Added Extra Hard Type IV Stone were obtained for the fabrication of wax patterns in the following conditions: without die spacer (G0), with one die spacer layer (G1); and with two die spacer layers (G2), with fifteen repetitions for each group. Each stone die was waxed and the wax patterns were invested as recommended by the manufacturer. Three wax patterns were embedded in each casting ring, each corresponding to a condition. Each coping, seated to the metal matrix by a Seating Pressure Standardizing Device (SPSD), was taken to the Optic Microscope for the measurement of marginal discrepancy. The obtained data (&micro;m) were submitted to statistical analysis (ANOVA) and Tukey test (p<0.05). There was not statistically significant difference among the materials VB II (93,40) and VB (118,73), and there was statistically significant different to Ti-cp (168,35) . In terms of the die spacer, there was a statistically significant difference among the three conditions (G0=177,31; G1=121,51 e G2=81,66). It was concluded that with two die spacer layers there is less marginal discrepancy.

Orientador: Guilherme de Siqueira Ferreira Anzaloni Saavedra / Coorientador: Lilian Costa Anami / Banca: Carlos Eduardo Francci / Banca: Clovis Pagani / Resumo: Este estudo avalia a influência da presença e tipo de pinos e núcleos na sobrevivência à fadiga de incisivos centrais restaurados com coroas totais. As coroas de 69 incisivos bovinos foram cortadas e as raízes tratadas endodonticamente. As raízes foram distribuídas aleatoriamente em três grupos (n = 23): núcleo de resina composta (NRC), núcleo de resina composta retido por pino de fibra de vidro (PFV) e núcleo metálico fundido (NMF). Todos receberam preparo de coroa total com férula de 2 mm, e então, uma coroa de cerâmica reforçada com leucita foi adesivamente cimentada. Três amostras de cada grupo foram testadas para determinação da carga máxima até a falha. As amostras restantes foram carregadas pelo teste acelerado de fadiga stepwise stress até a fratura ou suspensão após o término de 1,5 x 106 ciclos. A carga e o degrau em que cada espécime falhou foram analisadas pela estatística de Kaplan-Meier e Mantel-Cox (Log Rank test), seguidas por comparação múltipla aos pares, com nível de significância de 5%. O modo de falha foi analisado com estéreomicrocópio. Não houve diferença estatística entre os tratamentos quanto à carga (Mantel-Cox Log-Rank test for trend, X2=0,015, df=1, p=0,901), nem para o número de ciclos (Mantel-Cox Log-Rank test for trend, X2 =3,171, df=1, p=0,995). O modo de falha predominante foi a trinca da coroa. Fratura obliqua da raiz só foi observado nos grupos retidos por pinos. Nos incisivos tratados endodonticamente com férula de 2 mm, a presença e o tipo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract : This study evaluates the influence of presence and type of post-and-core systems on fatigue survival of non-vital central incisors restored with all-ceramic crowns. The crowns of 69 bovine incisors were cut and endodontically treated. The roots were randomly assigned into three groups (n=23): composite resin build-up (NRC), glass fiber post-retained-composite build-up (PFV) and cast post-and-core (NMF). All specimens received crown preparation with a 2 mm ferrule, and then a leucite-reinforced ceramic crown was adhesively cemented. Three samples from each group were tested for the determination of the maximum load to failure. The remaining samples were loaded by the accelerated fatigue stepwise stress test until fracture or suspension after the end of 1.5 x 106 cycles. The load and the step on which each specimen failed were analyzed by the Kaplan-Meier and Mantel-Cox (Log Rank test) statistics, followed by multiple paired comparisons, with a significance level of 5%. The failure mode was analyzed with stereomicroscope. There was no statistically significant difference between the treatments (Mantel-Cox Log-Rank test for trend, X2=0.015, df=1, p=0.901), nor for the number of cycles (Mantel-Cox Log-Rank test for trend, X2=3.171, df=1, p=0.995). The predominant failure mode was the crown crack. Oblique root fracture was observed only in groups retained by posts. The presence and type of post system did not influence the fatigue survival of the endodontically treated incisors with a 2 mm ferrule. Non-restorable fractures only occurred on teeth restored with posts...(Complete abstract click electronic access below) / Mestre

O objetivo do trabalho foi avaliar o efeito do uso de espaçadores na adaptação marginal de copings confeccionados em ligas de Ni-Cr (Verabond II) (VB II) e Ni-Cr-Be (Verabond) (VB) e Titânio cp (Tritan) (Ti-cp) fundidos pela técnica de cera perdida. A partir de uma matriz metálica, foram obtidos 135 troquéis de gesso resinado tipo IV para confecção dos padrões de cera nas seguintes condições: sem a presença de espaçador (G0), com uma camada de espaçador (G1) e com duas camadas de espaçador (G2), com quinze repetições para cada grupo. Foi realizado o enceramento de cada troquel e os padrões de cera foram incluídos em revestimento adequado para cada material. Em cada anel de fundição foram incluídos 3 padrões de cera, sendo cada um correspondente a cada condição. Cada coping, adaptado à matriz metálica por meio de um dispositivo padronizador da pressão de assentamento, foi levado ao Microscópio Óptico para aferição das medidas da desadaptação marginal. Os dados obtidos (&micro;m) foram submetidos à análise estatística (ANOVA) e teste de Tukey (p<0.05). Para a condição material, a liga VB (118,73) não apresentou diferença estatisticamente significante em relação à liga VB II (93,40), sendo que estas apresentaram diferença estatisticamente significante em relação ao Ti-cp (168,35). Em relação ao fator espaçador, houve diferença estatisticamente significante entre as três condições (G0=177,31; G1=121,51 e G2=81,66). Com base nos dados obtidos pelo presente estudo, pode-se afirmar que a presença de duas camadas de espaçador propicia menor desadaptação marginal. / The purpose of the study was to evaluate the effect of using die spacers on the marginal fit of Ni Cr (Verabond II) (VB II) and Ni-Cr-Be (Verabond) (VB) alloys and commercially pure Titanium (Tritan) (Ti-cp) casting copings by the lost wax technique. Using a metal master die, 135 Resin Added Extra Hard Type IV Stone were obtained for the fabrication of wax patterns in the following conditions: without die spacer (G0), with one die spacer layer (G1); and with two die spacer layers (G2), with fifteen repetitions for each group. Each stone die was waxed and the wax patterns were invested as recommended by the manufacturer. Three wax patterns were embedded in each casting ring, each corresponding to a condition. Each coping, seated to the metal matrix by a Seating Pressure Standardizing Device (SPSD), was taken to the Optic Microscope for the measurement of marginal discrepancy. The obtained data (&micro;m) were submitted to statistical analysis (ANOVA) and Tukey test (p<0.05). There was not statistically significant difference among the materials VB II (93,40) and VB (118,73), and there was statistically significant different to Ti-cp (168,35) . In terms of the die spacer, there was a statistically significant difference among the three conditions (G0=177,31; G1=121,51 e G2=81,66). It was concluded that with two die spacer layers there is less marginal discrepancy.

This study maps a way of looking at design history in New Zealand through the investigation of a taxon of industrially manufactured ceramics. Understanding design as an enfolded process of production, distribution, mediation and consumption, three threshold moments are identified as occurring within the European settlement period: the internationalisation of commodity production and consumption; the emergence of import substitution; and the deregulation of the market. While production has formed an element in the design of ceramics in New Zealand, it is contended that greater significance lies in both the trade and the mediation of these commodities and in particular in the way these have influenced local consumer choice. Emerging from this study, a series of key binaries become apparent: between the metropolitan centre and the frontier; between state and business; and between the traditional and the progressive. Likewise, the positioning of design within the institutionalised sites of power-or its absence from them-has been a prime force both in the development of manufacturing industry and in determining the nature of the consumer market.

Crown gall disease is an agricultural problem caused by the soil-borne bacterium, Agrobacterium tumefaciens. A. tumefaciens oncogenes cause transformed plant cells to overproduce the hormones, auxin and cytokinin. High hormone levels cause unorganized plant cell growth resulting in a gall. Control of crown gall disease is difficult because after plant cell transformation has occurred, the bacterium is no longer required for the disease to progress. Apple trees engineered to express double-stranded RNA of two A. tumefaciens oncogenes, ipt and iaaM, silenced the expression of the wild-type oncogenes and prevented crown gall disease. Only the iaaM oncogene was targeted for posttranscriptional gene silencing (PTGS) as measured by biological assays and by quantitative reverse-transcription polymerase chain reaction (q-RTPCR) on transgenic tissue. However, if the translation initiation sequence of the iaaM construction was eliminated, gall formation was not prevented, indicating that translatable RNA initiates silencing whereas untranslatable RNA does not. Other data indicate that the Arabidopsis thaliana micro-RNA pathway gene is involved in A. tumefaciens-mediated tumorigenesis. A. thaliana plants with a mutation in HEN1, a gene required for micro-RNA maturation, demonstrated a tenfold reduction in tumorigenesis upon A. tumefaciens infection compared to wild-type. The same plant line showed no difference in T-DNA transfer and nuclear uptake. / Graduation date: 2006

This thesis deals with the design of ligands for efficientasymmetric catalysis and studies of the conformation of theligands in the catalytically active complexes. All ligandsdeveloped contain chiral oxazoline heterocycles. The conformations of hydroxy- and methoxy-substitutedpyridinooxazolines and bis(oxazolines) during Pd-catalysedallylic alkylations were investigated using crystallography,2D-NMR techniques and DFT calculations. A stabilising OH-Pdinteraction was discovered which might explain the differencein reactivity between the hydroxy- and methoxy-containingligands. The conformational change in the ligands due to thisinteraction may explain the different selectivities observed inthe catalytic reaction. Polymer-bound pyridinooxazolines and bis(oxazolines) weresynthesised and employed in Pd-catalysed allylic alkylationswith results similar to those of monomeric analogues;enantioselectivities up to 95% were obtained. One polymer-boundligand could be re-used several times after removal of Pd(0).The polymer-bound bis(oxazoline) was also used in Zn-catalysedDiels-Alder reactions, but the heterogenised catalyst gavelower selectivities than a monomeric analogue. A series of chiral dendron-containing pyridinooxazolines andbis(oxazolines) were synthesised and evaluated in Pd-catalysedallylic alkylations. The dendrons did not seem to have anyinfluence on the selectivity and little influence on the yieldwhen introduced in the pyridinooxazoline ligands. In thebis(oxazoline) series lower generation dendrimers had a postiveon the selectivity, but the selectivity and the activitydecreased with increasing generation. Crown ether-containing ligands were investigated inpalladium-catalysed alkylations. No evidence of a possibleinteraction between the metal in the crown ether and thenucleophile was discovered. A new type of catalyst, an oxazoline-containing palladacyclewas found to be very active in oxidations of secondary alcoholsto the corresponding aldehydes or ketones. The reactions wereperformed with air as the re-oxidant. Therefore, this is anenviromentally friendly oxidation method. <b>Keywords:</b>asymmetric catalysis, chiral ligand,oxazolines, conformational study, allylic substitution,polymer-bound ligands, dendritic ligands, crown ether,oxidations, palladacycle.

The aim of this work is to study the interfacial properties of amphiphilic compounds at the liquid–air interface in an attempt to develop a comprehensive understanding of their orientation as well as the influence of their interaction with the solvent on the interfacial layer properties. Using Vibrational Sum Frequency Spectroscopy (VSFS) as the main tool, the molecular structure of the amphiphilic layer and the amphiphile–solvent relation can be illuminated in great detail – it is arguably the most sensitive surface spectroscopy currently available. Due to its second order nature, the VSFS technique is capable of distinguishing molecules at the interface even in the presence of a vast excess of similar molecules in the bulk.Ionic liquids (Ils) form a class of solvent which are increasingly receiving attention as ``green solvents´´. Some of these, such as ethyl ammonium nitrate (EAN), a protic IL, have the capacity to hydrogen bond extensively which is one of the important features they share with water. Since the interaction with solvent is an important consideration for self assembly and it is known that surfactant self assembly in the EAN bulk is analogous to in water, it was considered of interest to probe self assembly at EAN–air interface. To this end the interfacial structure of the pure EAN interface was probed, as was the conformation and ordering of nonionic surfactants. These studies reveal that EAN is highly ordered at the interface, exposing the ethyl moiety to the gas phase. Additionally, polarization studies have enabled the average orientation of the ethyl group to be determined. Adsorption of nonionic surfactants at the interface appears to significantly displace the EAN from the interface. The headgroup of the surfactant, a linear ethylene oxide group, appears to be highly disordered.The disorder of the linear ethylene oxide groups has led to difficulties in their surface spectroscopic fingerprinting in this and other works. In an attempt to study the interfacial behaviour of ethylene oxide and the temperature dependence of its hydration, closed loop structures of PEO attached to hydrophobic groups were also probed. This essentially locks their conformation. Such molecules are known as crown ethers and display interesting interfacial behaviour and also the ability to bind cations. The presence of even small amounts of adsorbed crown ethers at the water interface is shown to considerably perturb the water structure. The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation. The CH2 vibrational modes of crown ethers have been identified and found to be split due to their interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The orientation of Nitrobenzo crown (NB15C5) was monitored as a function of solution concentration, by targeting the ratio of peak intensities of the CN and NO2 vibrational modes. The water of hydration has also been probed as a function of crown concentration, salt concentration, and temperature. The latter study strongly suggests that the surface can be treated as a charged interface, and that the associated ordered water decreases with increasing ionic strength of the bulkFinally, insoluble monolayers of fatty acids spread on a water surface have also been studied in an effort to further understand the relationship between molecular architecture and film structure. Fatty acid (Arachidic Acid – AA and Eicosenoic Acid – EA) monolayers are compared to investigate the effect on the monolayer structure of introducing unsaturation into the alkyl chain. For AA, at very large area per molecule, floating domains of crystalline nature exist rather than any classical gaseous phase. The measured conformational disorder in EA decreases continuously with monolayer compression and no crystalline domains are observed at low density. Addition of NaCl to the subphase does not affect the monolayer order for either of the compounds; instead, a dramatic increase in the signal of the water hydrating the headgroups is observed. The effect of introducing further unsaturations (up to three) was also studied in order to probe the resulting interfacial structure. Remarkably the double bonds appear to adopt the same orientation, irrespective of how many they are in the chain. By monitoring the vinyl CH stretch it was possible to study the film stability towards oxidative degradation and it was found that all three unsaturated species studied showed rapid degradation. The rate of degradation could be controlled by adjusting the film pressure. However, the monolayers could be stabilised by performing the experiments in an inert nitrogen atmosphere. / QC20100629

This thesis is a report of the practical aspects and the problems of classification and documentation of a collection of memorabilias from the Crown Princess Couple's Wedding in Stockholm 2010. The collection contains 38 objects collected by Nordiska museet [The Nordic Museum], Sweden's largest museum of cultural history. Nordiska museet has a total collection of over 1,5 million items collected since 1873. My ambition in this thesis has been to describe my work with the classification and documentation of these new objects and their context. One of the main problems was how to combine the modern objects with the old existing collection within the two classification systems used at the museum. Four case studies were made toillustratethe different types ofproblems that occurred and the solutions found.I have also highlightedthe importance of being coherent when working with documentation and some of the consequences of classification.

<p>This thesis deals with the design of ligands for efficientasymmetric catalysis and studies of the conformation of theligands in the catalytically active complexes. All ligandsdeveloped contain chiral oxazoline heterocycles.</p><p>The conformations of hydroxy- and methoxy-substitutedpyridinooxazolines and bis(oxazolines) during Pd-catalysedallylic alkylations were investigated using crystallography,2D-NMR techniques and DFT calculations. A stabilising OH-Pdinteraction was discovered which might explain the differencein reactivity between the hydroxy- and methoxy-containingligands. The conformational change in the ligands due to thisinteraction may explain the different selectivities observed inthe catalytic reaction.</p><p>Polymer-bound pyridinooxazolines and bis(oxazolines) weresynthesised and employed in Pd-catalysed allylic alkylationswith results similar to those of monomeric analogues;enantioselectivities up to 95% were obtained. One polymer-boundligand could be re-used several times after removal of Pd(0).The polymer-bound bis(oxazoline) was also used in Zn-catalysedDiels-Alder reactions, but the heterogenised catalyst gavelower selectivities than a monomeric analogue.</p><p>A series of chiral dendron-containing pyridinooxazolines andbis(oxazolines) were synthesised and evaluated in Pd-catalysedallylic alkylations. The dendrons did not seem to have anyinfluence on the selectivity and little influence on the yieldwhen introduced in the pyridinooxazoline ligands. In thebis(oxazoline) series lower generation dendrimers had a postiveon the selectivity, but the selectivity and the activitydecreased with increasing generation.</p><p>Crown ether-containing ligands were investigated inpalladium-catalysed alkylations. No evidence of a possibleinteraction between the metal in the crown ether and thenucleophile was discovered.</p><p>A new type of catalyst, an oxazoline-containing palladacyclewas found to be very active in oxidations of secondary alcoholsto the corresponding aldehydes or ketones. The reactions wereperformed with air as the re-oxidant. Therefore, this is anenviromentally friendly oxidation method.</p><p><b>Keywords:</b>asymmetric catalysis, chiral ligand,oxazolines, conformational study, allylic substitution,polymer-bound ligands, dendritic ligands, crown ether,oxidations, palladacycle.</p>

Crinoids are the most primitive living members of the Phylum Echinodermata. Though still present in reduced numbers today, crinoids were the dominant echinoderms from the Ordovician to the Permian. The crinoid body plan consists of three major regions, the column, the calyx, and the arms. Each region serves important functions in crinoids. The column raises the rest of the body into the water column for more efficient feeding. The calyx contains the visceral mass and mouth. Arms extend out from the top of the calyx to trap microorgansisms and suspended organic particles in the water column. A re-evaluation of these functional units is undertaken to understand the importance of various structures and to obtain discrete characters for use in a cladistic analysis. The relationship of crinoid crown groups has been an active area of research for the past couple of decades. With each proposed phylogenetic relationship, a new interpretation of thecal plate homology has been proposed. Here each study is re-examined in the light of new data. A review of functional morphology indicates a dual-reference system to be the most supported interpretation of plate homology. The two reference points in this system are the stem-cup and the cup-arm junctions, at the top and bottom of the calyx. The difference between a two-circlet and three-circlet crinoid is the presence or absence of the middle (basal) circlet. A new cladistic analysis is presented, with the topology of trees obtained giving support for the retention of Paleozoic crinoid stem and crown groups. Crinoids appear abruptly in the fossil record. Questions pertaining to origins and ancestral stock abound. A biogeography study is employed to look at the distribution of crinoids from the Early to Middle Ordovician. Locality information, combined with an understanding of the movement of major plates, paleoclimate data, an understanding of larval distribution, and a review of similar studies carried out on different taxa, gives insight into possible radiation and dispersal patterns of crinoids from the first half of the Ordovician. / text