832 resultados para asymmetric transformation


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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Although an essential condition for the occurrence of human development, economic growth is not always efficiently converted into quality of life by nation-states. Accordingly, the objective of this study is to measure the social efficiency-the ability of a nation-state to convert its produced wealth into quality of life-of a set of 101 countries. To achieve this goal, the Data Envelopment Analysis method was used in its standard, cross-multiplicative and inverted form, by means of a new approach called 'triple index'. The main results indicated that the former Soviet republics and Eastern European countries stood out in terms of social efficiency. The developed countries, notwithstanding their high social indicators, did not excel in efficiency; however, the countries of south of Africa, despite having the worst social conditions, were also the most inefficient.

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The purpose of this research project is to analyze the Convergence Culture, a term coined by Henry Jenkins, to refer to the cultural transformation we are experiencing - people want to produce their own content, share their stories, expand their experiences and make connections to different platforms media. That is, individuals have changed their position once considered passive and accommodating to sustain an environment of intense involvement, construction and collective pursuit of new experiences. So that we could reach that culture converged, there was a paradigm shift from an asymmetric communication for communication increasingly bilateral. In this new scenario, communication to different audiences is based on a participatory and collaborative model in which organizations do not have absolute control over the media message. Therefore, this study tried to demonstrate what steps to be followed by public relations in convergence culture

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The reaction of [Pd{dmba}(l-N3)]2 (dmba = N,N-dimethylbenzylamine) with 1-(2-fluorophenyl)-3-(4- nitrophenyl)triazenido (L1 ) or 1,3-bis(4-nitrophenyl)triazenido (L2 ) anions, in methanol, and subsequent treatment with pyridine (py) allows the preparation of the corresponding cyclopalladated compounds [Pd(dmba)(L1 )(py)] (1) and [Pd(dmba)(L2 )(py)]py (2). The acentric mononuclear entities of (1) and (2) are connected by weak intermolecular non-classical CAHC hydrogen bonds, which results in 2-D arrangements by translation, along the [1 0 0] and [0 01] crystallographic directions, respectively.

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To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

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To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

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Statement of problem Because airborne-particle abrasion is an efficient method of improving the bond at the zirconia-cement interface, understanding its effect on the strength of yttria-stabilized tetragonal zirconia polycrystal is important. Purpose The purpose of this study was to evaluate the effect of the particle size used for airborne-particle abrasion on the flexural strength and phase transformation of a commercially available yttria-stabilized tetragonal zirconia polycrystal ceramic. Material and Methods For both flexural strength (20.0 × 4.0 × 1.2 mm) (n=14) and phase transformation (14.0-mm diameter × 1.3-mm thickness) (n=4), the zirconia specimens were made from Lava, and their surfaces were treated in the following ways: as-sintered (control); with 50-μm aluminum oxide (Al2O3) particles; with 120-μm Al2O3 particles; with 250-μm Al2O3 particles; with 30-μm silica-modified Al2O3 particles (Cojet Sand); with 120-μm Al2O3 particles, followed by 110-μm silica-modified Al2O3 particles (Rocatec Plus); and with Rocatec Plus. The phase transformation (%) was assessed by x-ray diffraction analysis. The 3-point flexural strength test was conducted in artificial saliva at 37°C in a mechanical testing machine. The data were analyzed by 1-way ANOVA and the Tukey honestly significant difference post hoc test (α=.05). Results Except for the Cojet Sand group, which exhibited statistically similar flexural strength to that of the as-sintered group and for the group abraded with 250-μm Al2O3 particles, which presented the lowest strength, airborne-particle abrasion with the other particle sizes provided the highest values, with no significant difference among them. The as-sintered specimens presented no monoclinic phase. The groups abraded with smaller particles (30 μm and 50 μm) and those treated with the larger ones (110 μm and/or 120 μm particles and 250 μm) exhibited percentages of monoclinic phase that varied from 4% to 5% and from 8.7% to 10%. Conclusions Except for abrasion with Cojet Sand, depending on the particle size, zirconia exhibited an increase or a decrease in its flexural strength. Airborne-particle abrasion promoted phase transformation (tetragonal to monoclinic), and the percentage of monoclinic phase varied according to the particle size.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Pós-graduação em Engenharia Elétrica - FEIS

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Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is unstable at temperatures above -100 °C and undergoes cycloreversion to produce the carbonyl oxide and carbonyl intermediates. These intermediates then recombine in another 1,3-electrocyclic addition step to form the 1,2,4-trioxolane or final ozonide. While the final ozonide is often isolable, most synthetic applications of ozonolysis require a subsequent reductive or oxidative step to form the desired carbonyl compound. During investigations into the nucleophilic trapping of the reactive carbonyl oxide, it was discovered that when amines were used as additives, an increased amount of reaction time was required in order to consume all of the starting material. Surprisingly, significant amounts of aldehydes and a suppression of ozonide formation also occurred which led to the discovery that amine N-oxides formed by the ozonation of the amine additives in the reaction were intercepting the carbonyl oxide. From the observed production of aldehydes, our proposed mechanism for the in situ reductive ozonolysis reaction with amine N-oxides involves the nucleophilic trapping of the carbonyl oxide intermediate to produce a zwitterionic adduct that fragments into 1O2, amine and the carbonyl thereby avoiding the formation of peroxidic intermediates. With the successful total syntheses of peroxyacarnoates A and D by Dr. Chunping Xu, the asymmetric total synthesis of peroxyplakorate A3 was investigated. The peroxyplakoric acids are cyclic peroxide natural products isolated from the Plakortis species of marine sponge that have been found to exhibit activity against malaria, cancer and fungi. Even though the peroxyplakorates differ from the peroxyacarnoates in the polyunsaturated tail and the head group, the lessons learned from the syntheses of the peroxyacarnoates have proven to be valuable in the asymmetric synthesis of peroxyplakorate A3. The challenges for the asymmetric synthesis of peroxyplakorate A3 include the stereospecific formation of the 3-methoxy-1,2-dioxane core with a propionate head group and the introduction of oxidation sensitive dienyl tail in the presence of a reduction sensitive 1,2-dioxane core. It was found that the stereochemistry of two of the chiral centers could be controlled by an anti-aldol reaction of a chiral propionate followed by the stereospecific intramolecular cyclization of a hydroperoxyacetal. The regioselective ozonolysis of a 1,2-disubstituted alkene in the presence of a terminal alkyne forms the required hydroperoxyacetal as a mixture of diastereomers. Finally, the dienyl tail is introduced by a hydrometallation/iodination of the alkyne to produce a vinyl iodide followed by a palladium catalyzed coupling reaction. While the coupling reaction was unsuccessful in these attempts, it is still believed that the intramolecular cyclization to introduce the 1,2-dioxane core could prove to be a general solution to many other cyclic peroxides natural products.

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Mashups are becoming increasingly popular as end users are able to easily access, manipulate, and compose data from several web sources. To support end users, communities are forming around mashup development environments that facilitate sharing code and knowledge. We have observed, however, that end user mashups tend to suffer from several deficiencies, such as inoperable components or references to invalid data sources, and that those deficiencies are often propagated through the rampant reuse in these end user communities. In this work, we identify and specify ten code smells indicative of deficiencies we observed in a sample of 8,051 pipe-like web mashups developed by thousands of end users in the popular Yahoo! Pipes environment. We show through an empirical study that end users generally prefer pipes that lack those smells, and then present eleven specialized refactorings that we designed to target and remove the smells. Our refactorings reduce the complexity of pipes, increase their abstraction, update broken sources of data and dated components, and standardize pipes to fit the community development patterns. Our assessment on the sample of mashups shows that smells are present in 81% of the pipes, and that the proposed refactorings can reduce that number to 16%, illustrating the potential of refactoring to support thousands of end users developing pipe-like mashups.

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Rhodium-catalyzed asymmetric hydroboration in conjunction with directing groups can be used control relative and absolute stereochemistry. Hydroboration has the potential to create new C–C, C–O, and C–N bonds from an intermediate C–B bond with retention of stereochemistry. Desymmetrization resulting in the loss of one or more symmetry elements can give rise to molecular chirality, i.e., the conversion of a prochiral molecule to one that is chiral. Unsaturated amides and esters hold the potential for two-point binding to the rhodium catalyst and have been shown to direct the regiochemistry and impact stereochemistry in asymmetric hydroborations of acyclic β,γ-unsaturated substrates. In the present study, the pendant amide functionality directs the hydroboration cis in the cyclic substrates studied; the corresponding ester substrates do so to a lesser extent. The enantioselectivity is determined by regioselective addition to the re or si site of the rhodium-complexed alkene. The effect of catalyst, ligand and borane on the observed diastereoselectivity and enantioselectivity for a variety of cyclopentenyl ester and amide substrates is discussed.