Processamento e propriedades magnéticas de manganitas multiferróicas = Mise en forme et propriétés magnétiques de manganites multiferróïques

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Correlation between pH and surface structural changes on human enamel submitted to different tooth whitening agents

The intense valuation of an esthetic pleasant smile guided the dentistry to bleached tooth due the popularity of whitening treatments. The consequence of it is an increasing interest in searching the effect of peroxides in hard dental tissues. The aim of this work was to analyze qualitatively in vitro the human enamel after three different bleaching treatments: Opalescence PF 10%, White Class 7.5% and Opalescence Xtra Boost 38%, correlating the structural changes in the surface of the enamel with its respective pH. A total of 40 sound human pre-molars were randomly divided into four groups of 10 elements, which had been immersed in artificial saliva during all the experiment. Bleaching protocols followed the recommendations of the respective manufacturers. Each bleached sample and control group were submitted to a scanning electronic microscopy analysis and compared with one another. Bleaching agents used in this experiment had modified the morphologic aspect of the surface of the dental enamel; however, it did not have correlation between the degrees of severity of the alterations and pH. There is a correlation between hydrogen peroxide concentration and changes in the enamel, where G4 showed more severe alterations, followed for G3 and G2.

Establishing common elements among some science education references as a resource to design a Didactics of Physics program for teachers initial education

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Local symmetries in gauge theories in a finite-dimensional setting

It is shown that the correct mathematical implementation of symmetry in the geometric formulation of classical field theory leads naturally beyond the concept of Lie groups and their actions on manifolds, out into the realm of Lie group bundles and, more generally, of Lie groupoids and their actions on fiber bundles. This applies not only to local symmetries, which lie at the heart of gauge theories, but is already true even for global symmetries when one allows for fields that are sections of bundles with (possibly) non-trivial topology or, even when these are topologically trivial, in the absence of a preferred trivialization. (C) 2012 Elsevier B.V. All rights reserved.

COMPLETE H-1 AND C-13 NMR STRUCTURAL ASSIGNMENTS FOR A GROUP OF FOUR GOYAZENSOLIDE-TYPE FURANOHELIANGOLIDES

Four goyazensolide-type sesquiterpene lactones - lychnofolide, centratherin, goyazensolide and goyazensolide acetate - were thoroughly studied by NMR experimental techniques. H-1 NMR, C-13 NMR {H-1}, COSY, HMQC, HMBC, J-res. and NOE experiments were performed to provide the needed structural information. Complete and unequivocal assignment, including the determination of all multiplicities, was obtained for each structure and the data collections are presented in tables.

Micro-structural and compositional variations of hydrothermal epidote-group minerals from a peralkaline granite, Corupá Pluton, Graciosa Province, South Brazil, and their petrological implications

Epidote-group minerals, together with albite, quartz, fluorite, Al-poor and Fe-rich phyllosilicates, zircon, and minor oxides and sulphides, are typical hydrothermal phases in peralkaline alkali-feldspar granites from the Corupá Pluton, Graciosa Province, South Brazil. The epidote-group minerals occur as single crystals and as aggregates filling in rock interstices and miarolitic cavities. They display complex recurrent zoning patterns with an internal zone of ferriallanite-(Ce), followed by allanite-(Ce), then epidote-ferriepidote, and an external zone with allanite-(Ce), with sharp limits, as shown in BSE and X-ray images. REE patterns show decreasing fractionation degrees of LREE over HREE from ferriallanite to epidote. The most external allanite is enriched in MREE. LA-ICP-MS data indicate that ferriallanite is enriched (>10-fold) in Ti, Sr and Ga, and depleted in Mg, Rb, Th and Zr relative to the host granite. Allanite has lower Ga and Mn and higher Zr, Nb and U contents as compared to ferriallanite, while epidote is enriched in Sr, U and depleted in Pb, Zr, Hf, Ti and Ga. The formation of these minerals is related to the variable concentrations of HFSE, Ca, Al, Fe and F in fluids remaining from magmatic crystallization, in an oxidizing environment, close to the HM buffer. L-MREE were in part released by the alteration of chevkinite, their main primary repository in the host rocks.

Complete ¹H and 13C NMR structural assignments for a group of four goyazensolide-type furanoheliangolides

Four goyazensolide-type sesquiterpene lactones - lychnofolide, centratherin, goyazensolide and goyazensolide acetate - were thoroughly studied by NMR experimental techniques. ¹H NMR, 13C NMR {¹H}, COSY, HMQC, HMBC, J-res. and NOE experiments were performed to provide the needed structural information. Complete and unequivocal assignment, including the determination of all multiplicities, was obtained for each structure and the data collections are presented in tables.

Inhibitors of Trypanosoma brucei trypanothione reductase: comparative molecular field analysis modeling and structural basis for selective inhibition

Background: Sleeping sickness is a major cause of death in Africa. Since no secure treatment is available, the development of novel therapeutic agents is urgent. In this context, the enzyme trypanothione reductase (TR) is a prominent molecular target that has been investigated in drug design for sleeping sickness. Results: In this study, comparative molecular field analysis models were generated for a series of Trypanosoma brucei TR inhibitors. Statistically significant results were obtained and the models were applied to predict the activity of external test sets, with good correlation between predicted and experimental results. We have also investigated the structural requirements for the selective inhibition of the parasite's enzyme over the human glutathione reductase. Conclusion: The quantitative structure-activity relationship models provided valuable information regarding the essential molecular requirements for the inhibitory activity upon the target protein, providing important insights into the design of more potent and selective TR inhibitors.

The Emergence of the Post-Socialist Welfare State - The Case of the Baltic States : Estonia, Latvia and Lithuania

This dissertation takes a step towards providing a better understanding of post-socialist welfare state development from a theoretical as well as an empirical perspective. The overall analytical goal of this thesis has been to critically assess the development of social policies in Estonia, Latvia and Lithuania using them as illustrative examples of post-socialist welfare state development in the light of the theories, approaches and typologies that have been developed to study affluent capitalist democracies. The four studies included in this dissertation aspire to a common aim in a number of specific ways. The first study tries to place the ideal-typical welfare state models of the Baltic States within the well-known welfare state typologies. At the same time, it provides a rich overview of the main social security institutions in the three countries by comparing them with each other and with the previous structures of the Soviet period. It examines the social insurance institutions of the Baltic States (old-age pensions, unemployment insurance, short-term benefits, sickness, maternity and parental insurance and family benefits) with respect to conditions of eligibility, replacement rates, financing and contributions. The findings of this study indicate that the Latvian social security system can generally be labelled as a mix of the basic security and corporatist models. The Estonian social security system can generally also be characterised as a mix of the basic security and corporatist models, even if there are some weak elements of the targeted model in it. It appears that the institutional changes developing in the social security system of Lithuania have led to a combination of the basic security and targeted models of the welfare state. Nevertheless, as the example of the three Baltic States shows, there is diversity in how these countries solve problems within the field of social policy. In studying the social security schemes in detail, some common features were found that could be attributed to all three countries. Therefore, the critical analysis of the main social security institutions of the Baltic States in this study gave strong supporting evidence in favour of identifying the post-socialist regime type that is already gaining acceptance within comparative welfare state research. Study Two compares the system of social maintenance and insurance in the Soviet Union, which was in force in the three Baltic countries before their independence, with the currently existing social security systems. The aim of the essay is to highlight the forces that have influenced the transformation of the social policy from its former highly universal, albeit authoritarian, form, to the less universal, social insurance-based systems of present-day Estonia, Latvia and Lithuania. This study demonstrates that the welfare–economy nexus is not the only important factor in the development of social programs. The results of this analysis revealed that people's attitudes towards distributive justice and the developmental level of civil society also play an important part in shaping social policies. The shift to individualism in people’s mentality and the decline of the labour movement, or, to be more precise, the decline in trade union membership and influence, does nothing to promote the development of social rights in the Baltic countries and hinders the expansion of social policies. The legacy of the past has been another important factor in shaping social programs. It can be concluded that social policy should be studied as if embedded not only in the welfare-economy nexus, but also in the societal, historical and cultural nexus of a given society. Study Three discusses the views of the state elites on family policy within a wider theoretical setting covering family policy and social policy in a broader sense and attempts to expand this analytical framework to include other post-socialist countries. The aim of this essay is to explore the various views of the state elites in the Baltics concerning family policy and, in particular, family benefits as one of the possible explanations for the observed policy differences. The qualitative analyses indicate that the Baltic States differ significantly with regard to the motives behind their family policies. Lithuanian decision-makers seek to reduce poverty among families with children and enhance the parents’ responsibility for bringing up their children. Latvian policy-makers act so as to increase the birth rate and create equal opportunities for children from all families. Estonian policy-makers seek to create equal opportunities for all children and the desire to enhance gender equality is more visible in the case of Estonia in comparison with the other two countries. It is strongly arguable that there is a link between the underlying motives and the kinds of family benefits in a given country. This study, thus, indicates how intimately the attitudes of the state bureaucrats, policy-makers, political elite and researchers shape social policy. It confirms that family policy is a product of the prevailing ideology within a country, while the potential influence of globalisation and Europeanisation is detectable too. The final essay takes into account the opinions of welfare users and examines the performances of the institutionalised family benefits by relying on the recipients’ opinions regarding these benefits. The opinions of the populations as a whole regarding government efforts to help families are compared with those of the welfare users. Various family benefits are evaluated according to the recipients' satisfaction with those benefits as well as the contemporaneous levels of subjective satisfaction with the welfare programs related to the absolute level of expenditure on each program. The findings of this paper indicate that, in Latvia, people experience a lower level of success regarding state-run family insurance institutions, as compared to those in Lithuania and Estonia. This is deemed to be because the cash benefits for families and children in Latvia are, on average, seen as marginally influencing the overall financial situation of the families concerned. In Lithuania and Estonia, the overwhelming majority think that the family benefit systems improve the financial situation of families. It appears that recipients evaluated universal family benefits as less positive than targeted benefits. Some universal benefits negatively influenced the level of general satisfaction with the family benefits system provided in the countries being researched. This study puts forward a discussion about whether universalism is always more legitimate than targeting. In transitional economies, in which resources are highly constrained, some forms of universal benefits could turn out to be very expensive in relative terms, without being seen as useful or legitimate forms of help to families. In sum, by closely examining the different aspects of social policy, this dissertation goes beyond the over-generalisation of Eastern European welfare state development and, instead, takes a more detailed look at what is really going on in these countries through the examples of Lithuania, Latvia and Estonia. In addition, another important contribution made by this study is that it revives ‘western’ theoretical knowledge through ‘eastern’ empirical evidence and provides the opportunity to expand the theoretical framework for post-socialist societies.

Structural and functional characterization of Group B Streptococcus class C sortases

In Group B Streptococcus (GBS) three structurally distinct types of pili have been discovered as potential virulence factors and vaccine candidates. The pilus-forming proteins are assembled into high-molecular weight polymers via a transpeptidation mechanism mediated by specific class C sortases. Using a multidisciplinary approach including bioinformatics, structural and biochemical studies and in vivo mutagenesis we performed a broad characterization of GBS sortase C. The high resolution X-ray structure of the enzymes revealed that the active site, located into the β-barrel core of the enzyme, is made of the catalytic triad His157-Cys219-Arg228 and covered by a loop, known as the “lid”. We show that the catalytic triad and the predicted N- and C-terminal trans-membrane regions are required for the enzyme activity. Interestingly, by in vivo complementation mutagenesis studies we found that the deletion of the entire lid loop or mutations in specific lid key residues had no effect on catalytic activity of the enzyme. In addition, kinetic characterizations of recombinant enzymes indicate that the lid mutants can still recognize and cleave the substrate-mimicking peptide at least as well as the wild type protein.

Synthesis of Modified Amino Acids and Insertion in Peptides and Mimetics. Structural Aspects and Impact on Biological Activity.

I studied the effects exerted by the modifications on structures and biological activities of the compounds so obtained. I prepared peptide analogues containing unusual amino acids such as halogenated, alkylated (S)- or (R)-tryptophans, useful for the synthesis of mimetics of the endogenous opioid peptide endomorphin-1, or 2-oxo-1,3-oxazolidine-4-carboxylic acids, utilized as pseudo-prolines having a clear all-trans configuration of the preceding peptide bond. The latter gave access to a series of constrained peptidomimetics with potential interest in medicinal chemistry and in the field of the foldamers. In particular, I have dedicated much efforts to the preparation of cyclopentapeptides containing D-configured, alfa-, or beta-aminoacids, and also of cyclotetrapeptides including the retro-inverso modification. The conformational analyses confirmed that these cyclic compounds can be utilized as rigid scaffolds mimicking gamma- or beta-turns, allowing to generate new molecular and 3D diversity. Much work has been dedicated to the structural analysis in solution and in the receptor-bound state, fundamental for giving a rationale to the experimentally determined bioactivity, as well as for predicting the activity of virtual compounds (in silico pre-screen). The conformational analyses in solution has been done mostly by NMR (2D gCosy, Roesy, VT, molecular dynamics, etc.). A special section is dedicated to the prediction of plausible poses of the ligands when bound to the receptors by Molecular Docking. This computational method proved to be a powerful tool for the investigation of ligand-receptor interactions, and for the design of selective agonists and antagonists. Another practical use of cyclic peptidomimetics was the synthesis and biological evaluation of cyclic analogues of endomorphin-1 lacking in a protonable amino group. The studies revealed that a inverse type II beta-turn on D-Trp-Phe constituted the bioactive conformation.

Geochemistry, petrogenesis and tectonic setting of ophiolites and mafic-ultramafic complexes in the Northeastern Aegean Region

In this study two ophiolites and a mafic-ultramafic complexes of the northeastern Aegean Sea, Greece, have been investigated to re-evaluate their petrogenetic evolution and tectonic setting. These complexes are: the mafic-ultramafic complex of Lesvos Island and the ophiolites of Samothraki Island and the Evros area. In order to examine these complexes in detail whole-rock major- and trace-elements as well as Sr and Nd isotopes, and minerals were analysed and U-Pb SHRIMP ages on zircons were determined. The mafic-ultramafic complex of Lesvos Island consists of mantle peridotite thrusted over a tectonic mélange containing metasediments, metabasalts and a few metagabbros. This succession had previously been interpreted as an ophiolite of Late Jurassic age. The new field and geochemical data allow a reinterpretation of this complex as representing an incipient continental rift setting that led to the subsequent formation of the Meliata-Maliac-Vardar branches of Neotethys in Upper Permian times (253 ± 6 Ma) and the term “Lesvos ophiolite” should be abandoned. With proceeding subduction and closure of the Maliac Ocean in Late Jurassic times (155 Ma) the Lesvos mafic-ultramafic complex was obducted. Zircon ages of 777, 539 and 338 Ma from a gabbro strongly suggest inheritance from the intruded basement and correspond to ages of distinct terranes recently recognized in the Hellenides (e.g. Florina terrane). Geochemical similar complexes which contain rift associations with Permo-Triassic ages can be found elsewhere in Greece and Turkey, namely the Teke Dere Thrust Sheet below the Lycian Nappes (SW Turkey), the Pindos subophiolitic mélange (W Greece), the Volcanosedimentary Complex on Central Evia Island (Greece) and the Karakaya Complex (NW Turkey). This infers that the rift-related rocks from Lesvos belong to an important Permo-Triassic rifting episode in the eastern Mediterranean. The ‘in-situ’ ophiolite of Samothraki Island comprises gabbros, sparse dykes and basalt flows as well as pillows cut by late dolerite dykes and had conventionally been interpreted as having formed in an ensialic back-arc basin. The results of this study revealed that none of the basalts and dolerites resemble mid-ocean ridge or back-arc basin basalts thus suggesting that the Samothraki ophiolite cannot represent mature back-arc basin crust. The age of the complex is regarded to be 160 ± 5 Ma (i.e. Oxfordian; early Upper Jurassic), which precludes any correlation with the Lesvos mafic-ultramafic complex further south (253 ± 6 Ma; Upper Permian). Restoration of the block configuration in NE Greece, before extensional collapse of the Hellenic hinterland and exhumation of the Rhodope Metamorphic Core Complex (mid-Eocene to mid-Miocene), results in a continuous ophiolite belt from Guevgueli in the NW to Samothraki in the SE, thus assigning the latter to the Innermost Hellenic Ophiolite Belt. In view of the data of this study, the Samothraki ophiolite represents a rift propagation of the Sithonia ophiolite spreading ridge into the Chortiatis calc-alkaline arc. The ophiolite of the Evros area consists of a plutonic sequence comprising cumulate and non-cumulate gabbros with plagiogranite veins, and an extrusive sequence of basalt dykes, massive and pillow lavas as well as pyroclastic rocks. Furthermore, in the Rhodope Massif tectonic lenses of harzburgites and dunites can be found. All rocks are spatially separated. The analytical results of this study revealed an intra-oceanic island arc setting for the Evros ophiolitic rocks. During late Middle Jurassic times (169 ± 2 Ma) an intra-oceanic arc has developed above a northwards directed intra-oceanic subduction zone of the Vardar Ocean in front of the Rhodope Massif. The boninitic, island arc tholeiitic and calc-alkaline rocks reflect the evolution of the Evros island arc. The obduction of the ophiolitic rocks onto the Rhodope basement margin took place during closure of the Vardar ocean basins. The harzburgites and dunites of the Rhodope Massif are strongly depleted and resemble harzburgites from recent oceanic island arcs. After melt extraction they underwent enrichment processes by percolating melts and fluids from the subducted slab. The relationship of the peridotites and the Evros ophiolite is still ambiguous, but the stratigraphic positions of the peridotites and the ophiolitic rocks indicate separated origin. The harzburgites and dunites most probably represent remnants of the mantle wedge of the island arc of the Rhodope terrane formed above subducted slab of the Nestos Ocean in late Middle Jurassic times. During collision of the Thracia terrane with the Rhodope terrane thrusting of the Rhodope terrane onto the Thracia terrane took place, whereas the harzburgites and dunites were pushed between the two terranes now cropping out on top of the Thracia terrane of the Rhodope Massif.