Molecular Basis of the Thermostability and Thermophilicity of Laminarinases: X-ray Structure of the Hyperthermostable Laminarinase from Rhodothermus marinus and Molecular Dynamics Simulations

Glycosyl hydrolases are enzymes capable of breaking the glycosidic linkage of polysaccharides and have considerable industrial and biotechnological applications. Driven by the later applications, it is frequently desirable that glycosyl hydrolases display stability and activity under extreme environment conditions, such as high temperatures and extreme pHs. Here, we present X-ray structure of the hyperthermophilic laminarinase from Rhodothermus marinus (RmLamR) determined at 1.95 angstrom resolution and molecular dynamics simulation studies aimed to comprehend the molecular basis, for the thermal stability of this class of enzymes. As most thermostable proteins, RmLamR contains a relatively large number of salt bridges, which are not randomly distributed on the structure. On the contrary, they form clusters interconnecting beta-sheets of the catalytic domain. Not all salt bridges, however, are beneficial for the protein thermostability: the existence of charge-charge interactions permeating the hydrophobic core of the enzymes actually contributes to destabilize the structure by facilitating water penetration into hydrophobic cavities, as can be seen in the case of mesophilic enzymes. Furthermore, we demonstrate that the mobility of the side-chains is perturbed differently in each class of enzymes. The side-chains of loop residues surrounding the catalytic cleft in the mesophilic laminarinase gain mobility and obstruct the active site at high temperature. By contrast, thermophilic laminarinases preserve their active site flexibility, and the active-site cleft remains accessible for recognition of polysaccharide substrates even at high temperatures. The present results provide structural insights into the role played by salt-bridges and active site flexibility on protein thermal stability and may be relevant for other classes of proteins, particularly glycosyl hydrolases.

A DISCRETIZATION SCHEME FOR AN ONE-DIMENSIONAL REACTION-DIFFUSION EQUATION WITH DELAY AND ITS DYNAMICS

The goal of this paper is to present an approximation scheme for a reaction-diffusion equation with finite delay, which has been used as a model to study the evolution of a population with density distribution u, in such a way that the resulting finite dimensional ordinary differential system contains the same asymptotic dynamics as the reaction-diffusion equation.

Docking and molecular dynamics simulation of quinone compounds with trypanocidal activity

In this work, two different docking programs were used, AutoDock and FlexX, which use different types of scoring functions and searching methods. The docking poses of all quinone compounds studied stayed in the same region in the trypanothione reductase. This region is a hydrophobic pocket near to Phe396, Pro398 and Leu399 amino acid residues. The compounds studied displays a higher affinity in trypanothione reductase (TR) than glutathione reductase (GR), since only two out of 28 quinone compounds presented more favorable docking energy in the site of human enzyme. The interaction of quinone compounds with the TR enzyme is in agreement with other studies, which showed different binding sites from the ones formed by cysteines 52 and 58. To verify the results obtained by docking, we carried out a molecular dynamics simulation with the compounds that presented the highest and lowest docking energies. The results showed that the root mean square deviation (RMSD) between the initial and final pose were very small. In addition, the hydrogen bond pattern was conserved along the simulation. In the parasite enzyme, the amino acid residues Leu399, Met400 and Lys402 are replaced in the human enzyme by Met406, Tyr407 and Ala409, respectively. In view of the fact that Leu399 is an amino acid of the Z site, this difference could be explored to design selective inhibitors of TR.

Speak Good English Movement in Singapore : Reactions in Social and Traditional Media

The first Speak Good English Movement, SGEM, took place in 2000, and has been organized annually ever since. Speaking a “standard” form of English is considered to bring increased personal power. However, the SGEM wants the Singaporeans to use “standard” English in their private life as well. A decade after the beginning of the campaign, a Speak Good Singlish Movement was started. Based on studies of language and identity, it is understandable why some Singaporeans might feel the SGEM threatens their identity. However, the reactions towards the campaign are mainly positive. For the purposes of this analysis, Twitter messages, Facebook pages, and newspaper articles from The Straits Times were collected. The SGEM has hailed both direct and indirect praise and criticism in both social and traditional media: Five newspaper articles praise the campaign while five criticize it; the results are nine and seven respectively for social media. This thesis looks at reactions towards the SGEM in both social and traditional media, analyzes how these reactions might relate to the ideas of the power of language, its variety and the relation of language and identity.

Unlicensed personnel administering medications to older persons living at home : a challenge for social and care services

BACKGROUND: Administration of medication to care recipients is delegated to home-care assistants working in the municipal social care, alongside responsibility for providing personal assistance for older people. Home-care assistants have practical administration skills, but lack formal medical knowledge. AIM: The aim of this study was to explore how home-care assistants perceive administration of medication to older people living at home, as delegated to them in the context of social care. METHODS: Four focus groups consisting of 19 home-care assistants were conducted. Data were analysed using qualitative content analysis. RESULTS: According to home-care assistants, health and social care depends on delegation arrangements to function effectively, but in the first place it relieves a burden for district nurses. Even when the delegation had expired, administration of medication continued, placing the statutes of regulation in a subordinate position. There was low awareness among home-care assistants about the content of the statutes of delegation. Accepting delegation to administer medications has become an implicit prerequisite for social care work in the municipality. CONCLUSIONS: Accepting the delegation to administer medication was inevitable and routine. In practice, the regulating statute is made subordinate and consequently patient safety can be threatened. The organisation of health and social care relies on the delegation arrangement to meet the needs of a growing number of older home-care recipients. IMPLICATIONS FOR PRACTICE: This is a crucial task which management within both the healthcare professions and municipal social care needs to address, to bridge the gap between statutes and practice, to create arenas for mutual collaboration in the care recipients' best interest and to ensure patient safety.

Property rights as a public policy tool: an empirical analysis of the social and economic effects

Secure property rights are considered a key determinant of economic development. However, the evaluation of the causal effects of land titling is a difficult task. The Brazilian government through a program called "Papel Passado" has issued titles, since 2004, to over 85,000 families and has the goal to reach 750,000. Furthermore, another topic in Public Policy that is crucial to developing economies is income generation and child labor force participation. Particularly, in Brazil, about 5.4 million children and teenagers between 5 and 17 years old are still working. This thesis examines the direct impact of securing a property title on income and child labor force participation. In order to isolate the causal role of ownership security, this study uses a comparison between two close and very similar communities in the City of Osasco case (a town with 650,000 people in the São Paulo metropolitan area). One of them, Jardim Canaã, was fortunated to receive the titles in 2007, the other, Jardim DR, given fiscal constraints, only will be part of the program schedule in 2012, and for that reason became the control group. Also, this thesis also aims to test if there is any relationship between land title and happiness. The estimates suggest that titling results in a substantial decrease of child labor force participation, increase of income and happiness for the families that received the title compared to the others.

Social and entrepreneurial values profiles

O empreendedor tem intrigado acadêmicos há anos. Portanto, inúmeras abordagens têm sido aplicadas para entender quem é o empreendedor, sua personalidade e comportamentos. As principais escolas de estudo sobre o tema são a escola de traços psicológicos e a escola de processos ou comportamentos. No entanto, a academia ainda carece de uma definição concreta do indivíduo responsável pelo fenômeno do empreendedorismo. Em uma tentativa de esclarecer essa questão esta pesquisa sugere uma nova abordagem para a compreensão da pessoa do empreendedor com base nos valores pessoais de Schwartz. O objetivo da tese é compreender o perfil de valores de empreendedores sociais e comerciais a fim de determinar as semelhanças e diferenças nas suas preferências de valores que orientam o comportamento empreendedor de ambos e o enfoque social de um e privado do outro. Para este fim a versão mais curta do Questionário de Perfil Valores de Schwartz foi aplicada a uma amostra de 44 empreendedores sociais e 71 comerciais. A primeira proposição da tese era que os empreendedores sociais e comerciais possuiriam um perfil de valores. A segunda era que este perfil de valores seria determinado pelo princípio organizador da ansiedade com preferência pelos valores “livres de ansiedade” em decorrência das características empreendedoras que enfatizam busca pela auto-expansão, crescimento e promoção do alcance de metas. Dessa forma os valores mais importantes para ambos os tipos de empreendedores seriam auto-determinação, estimulação, hedonismo, universalismo e benevolência. A terceira proposição era que os empreendedores sociais e comerciais atribuiriam a mais alta importância ao valor auto-determinação. A quarta propunha que os empreendedores sociais dariam maior importância do que os comerciais para benevolência e universalismo visto que esses valores presumem apreciação pelos outros, preservação e valorização do bem-estar das pessoas mais próximas bem como de qualquer ser vivo em geral. Os resultados das análises descritivas e dos testes de hipóteses apontam para a validação de todas as proposições menos a última. No entanto, apesar da quarta proposição não haver sido estatisticamente comprovada, houve uma leve tendência dos empreendedores sociais darem maior importância do que os comerciais aos valores de auto-transcendência. Conseqüentemente, para maiores esclarecimentos sobre esse tópico, outros estudos com amostras maiores e randômicas devem ser realizadas.

Wealth composition, endogenous fertility and the dynamics of income inequality

This paper analyzes how differences in the composition of wealth between human and physical capital among families affect fertility choices. These in tum influence the dynamics of wealth and income inequality across generations through a tradeoffbetween quantity and quality of children. Wealth composition affects fertility because physical capital has only a wealth effect on number of children, whereas human capital increases the time cost of child-rearing in addition to the wealth effect. I construct a model combining endogenous fertility with borrowing constraints in human capital investments, in which weaIth composition is determined endogenously. The model is calibrated to the PNAD, a Brazilian household survey, and the main findings of the paper can be summarized as follows. First, the model implies that the crosssection relationship between fertility and wealth typically displays a U-shaped pattem, reflecting differences in wealth composition between poor and rich families. Also, the quantity-quality tradeoff implies a concave cross-section relationship between investments per child and wealth. Second, as the economy develops and families overcome their bOlTowing constraints, the negative effect of weaIth on fertility becomes smaller, and persistence of inequality declines accordingly. The empirical evidence presented in this paper is consistent with both implications .

Quasi-experimental estimates of fiscal spillovers and spatial interactions among Brazilian cities

Nós usamos a metodologia de Regressões em Descontinuidade (RDD) para estimar o efeito causal do Fundo de Participação dos Municípios (FPM) recebido por um município sobre características dos municípios vizinhos, considerando uma variedade de temas: finanças públicas, educação, saúde e resultados eleitorais. Nós exploramos a regra que gera uma variação exógena da transferência em munícipios próximos às descontinuidades no repasse do fundo de acordo com faixas de população. Nossa principal contribuição é estimar separadamente e em conjunto o efeito spillover e o efeito direto do FPM, considerando ambos municípios vizinhos ou apenas um deles próximos às mudanças de faixa. Dessa forma, conseguimos entender melhor a interação entre municípios vizinhos quando há uma correlação na probabilidade de receber uma transferência federal. Nós mostramos que a estimativa do efeito direto do FPM sobre os gastos locais diminui em cerca de 20% quando controlamos pelo spillover do vizinho, que em geral é positivo, com exceção dos gastos em saúde e saneamento. Nós estimamos um efeito positivo da transferência sobre notas na prova Brasil e taxas de aprovação escolares em municípios vizinhos e na rede estadual do ensino fundamental. Por outro lado, o recebimento de FPM por municípios vizinhos de pequena população reduz o provimento de bens e serviços de saúde em cidades próximas e maiores, o que pode ocorrer devido à redução da demanda por serviços de saúde. A piora de alguns indicadores globais de saúde é um indício, no entanto, de que podem existir problemas de coordenação para os prefeitos reterem seus gastos em saúde. De fato, quando controlamos pela margem de vitória nas eleições municipais e consideramos apenas cidades vizinhas com prefeitos de partido diferentes, o efeito spillover é maior em magnitude, o que indica que incentivos políticos são importantes para explicar a subprovisão de serviços em saúde, por um lado, e o aumento da provisão de bens em educação, por outro. Nós também constatamos um efeito positivo do FPM sobre votos para o partido do governo federal nas eleições municipais e nacionais, e grande parte desse efeito é explicado pelo spillover do FPM de cidades vizinhas, mostrando que cidades com dependência econômica do governo federal se tornam a base de sustentação e apoio político desse governo. Por fim, nós encontramos um efeito ambíguo do aumento de receita devido ao FPM sobre a competição eleitoral nas eleições municipais, com uma queda da margem de vitória do primeiro colocado e uma redução do número de candidatos, o que pode ser explicado pelo aumento do custo fixo das campanhas locais.

Configurando a cidade contemporânea em Natal : os processos espaciais em Ponta Negra

This dissertation is about the spatial configuration in Natal and processes in the Ponta Negra neighborhood today. Ponta Negra has undergone a number of critical social and spatial changes due to tourism development after the 1990s. It is of special interest to consider the intensification of real estate investment after 2000, when the new airport terminal, located in the neighboring municipality of Parnamirim, was in use. Ponta Negra is the place where most tourists go to, so attracting considerable public investments. New agents of transformation have produced change in the neighborhood as well. The present study aims at analysing the spatial processes in this part of the city. Here, the spatial configuration that resulted from extended real estate investments, both public and private, in recent years, is analysed in detail. The study identifies the multually differentiated, however internally homogenous areas. The concepts of production of space, contemporanean urban development and spatial dynamics are discussed. The research is based on document analysis and field work. Results were plotted to maps and tables. A detailed analysis of the spatial processes in the Ponta Negra neighborhood is undertaken as a conclusion, considering the contemporanean global scenario

Transfer function-noise modeling and spatial interpolation to evaluate the risk of extreme (shallow) water-table levels in the Brazilian Cerrados

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Reproductive migration and population dynamics of the blue crab Callinectes danae in an estuary in southeastern Brazil

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