Structural role of fluoride in the ion-conducting glass system B(2)O(3)-PbO-LiF studied by single- and double-resonance NMR

The local structure of an ion-conducting glass with nominal composition 50B(2)O(3)-10PbO-40LiF has been investigated by complementary (7)Li, (11)B, (19)F, and (207)Pb single- and double-resonance experiments. The results give insight into the structural role of the lithium fluoride additive in borate glasses: (1) LiF is seen to actively participate in the network transformation process contributing to the conversion of three- into four-coordinate boron units, as shown by (11)B single-resonance as well as by (11)B{(19)F} and (19)F{(11)B} double-resonance experiments. (2) (19)F signal quantification experiments suggest substantial fluoride loss, presumably caused by formation of volatile BF(3). A part of the fluoride remains in the dopant role, possibly in the form of small LiF-like cluster domains, which serve as a mobile ion supply. (3) The extent of lithium-fluorine and lead-fluorine interactions has been characterized by (7)Li{(19)F} and (207)Pb{(19)F} REDOR and SEDOR experiments. On the basis of these results, a quantitative structural description of this system has been developed.

The first group (co)homology of a group G with coefficients in some G-modules

Let G be a group. We give some formulas for the first group homology and cohomology of a group G with coefficients in an arbitrary G-module (Z) over tilde. More explicit calculations are done in the special cases of free groups, abelian groups and nilpotent groups. We also perform calculations for certain G-module M, by reducing it to the case where the coefficient is a G-module (Z) over tilde. As a result of the well known equalities H-1(X, M) = H-1(pi(1)(X), M) and H-1(X, M) = H-1(pi(1) (X), M), for any G-module M, we are able to calculate the first homology and cohomology groups of topological spaces with certain local system of coefficients.

Minimal Lagrangian surfaces in the tangent bundle of a Riemannian surface

Given an oriented Riemannian surface (Sigma, g), its tangent bundle T Sigma enjoys a natural pseudo-Kahler structure, that is the combination of a complex structure 2, a pseudo-metric G with neutral signature and a symplectic structure Omega. We give a local classification of those surfaces of T Sigma which are both Lagrangian with respect to Omega and minimal with respect to G. We first show that if g is non-flat, the only such surfaces are affine normal bundles over geodesics. In the flat case there is, in contrast, a large set of Lagrangian minimal surfaces, which is described explicitly. As an application, we show that motions of surfaces in R(3) or R(1)(3) induce Hamiltonian motions of their normal congruences, which are Lagrangian surfaces in TS(2) or TH(2) respectively. We relate the area of the congruence to a second-order functional F = f root H(2) - K dA on the original surface. (C) 2010 Elsevier B.V. All rights reserved.

DMSO-Induced Denaturation of Hen Egg White Lysozyme

We report on the size, shape, structure, and interactions of lysozyme in the ternary system lysozyme/DMSO/water at low protein concentrations. Three structural regimes have been identified, which we term the ""folded"" (0 < phi(DMSO) < 0.7), ""unfolded"" (0.7 <= phi(DMSO) < 0.9), and ""partially collapsed"" (0.9 <= phi(DMSO) < 1.0) regime. Lysozyme resides in a folded conformation with an average radius of gyration of 1.3 +/- 0.1 nm for phi(DMSO) < 0.7 and unfolds (average R(g) of 2.4 +/- 0.1 nm) above phi(DMSO) > 0.7. This drastic change in the protein`s size coincides with a loss of the characteristic tertiary structure. It is preceded by a compaction of the local environment of the tryptophan residues and accompanied by a large increase in the protein`s overall flexibility. In terms of secondary structure, there is a gradual loss of alpha-helix and concomitant increase of beta-sheet structural elements toward phi(DMSO) = 0.7, while an increase in phi(DMSO) at even higher DMSO volume fractions reduces the presence of both a-helix and beta-sheet secondary structural elements. Protein-protein interactions remain overall repulsive for all values of phi(DMSO) An attempt is made to relate these structural changes to the three most important physical mechanisms that underlie them: the DMSO/water microstructure is strongly dependent on the DMSO volume fraction, DMSO acts as a strong H-bond acceptor, and DMSO is a bad solvent for the protein backbone and a number of relatively polar side groups, but a good solvent for relatively apolar side groups, such as tryptophan.

Effects of hydroxyl group distribution on the reactivity, stability and optical properties of fullerenols

We investigate the impact of hydroxyl groups on the properties of C(60)(OH)(n) systems, with n = 1, 2, 3, 4, 8, 10, 16, 18, 24, 32 and 36 by means of first-principles density functional theory calculations. A detailed analysis from the local density of states has shown that adsorbed OH groups can induce dangling bonds in specific carbon atoms around the adsorption site. This increases the tendency to form polyhydroxylated fullerenes (fullerenols). The structural stability is analyzed in terms of the calculated formation enthalpy of each species. Also, a careful examination of the electron density of states for different fullerenols shows the possibility of synthesizing single molecules with tunable optical properties.

Volunteered Geographic Information For Water Management: A Prototype Architecture

Driven by Web 2.0 technology and the almost ubiquitous presence of mobile devices, Volunteered Geographic Information (VGI) is knowing an unprecedented growth. These notable technological advancements have opened fruitful perspectives also in the field of water management and protection, raising the demand for a reconsideration of policies which also takes into account the emerging trend of VGI. This research investigates the opportunity of leveraging such technology to involve citizens equipped with common mobile devices (e.g. tablets and smartphones) in a campaign of report of water-related phenomena. The work is carried out in collaboration with ADBPO - Autorità di bacino del fiume Po (Po river basin Authority), i.e. the entity responsible for the environmental planning and protection of the basin of river Po. This is the longest Italian river, spreading over eight among the twenty Italian Regions and characterized by complex environmental issues. To enrich ADBPO official database with user-generated contents, a FOSS (Free and Open Source Software) architecture was designed which allows not only user field-data collection, but also data Web publication through standard protocols. Open Data Kit suite allows users to collect georeferenced multimedia information using mobile devices equipped with location sensors (e.g. the GPS). Users can report a number of environmental emergencies, problems or simple points of interest related to the Po river basin, taking pictures of them and providing other contextual information. Field-registered data is sent to a server and stored into a PostgreSQL database with PostGIS spatial extension. GeoServer provides then data dissemination on the Web, while specific OpenLayers-based viewers were built to optimize data access on both desktop computers and mobile devices. Besides proving the suitability of FOSS in the frame of VGI, the system represents a successful prototype for the exploitation of user local, real-time information aimed at managing and protecting water resources.

Coordenação interinstitucional para o desenvolvimento local: um estudo em Araçuaí, Minas Gerais

This essay aims to discuss local development under the prospect of coordinated intervention of multiple organizations, considering different thematic areas of action, different economic sectors and regions of origin; structured in different methodologies and owners of different social technologies field of expertises. Search to identify determinants, facilitators, and restrictive factors of cross sectorial and cross organizational coordination processes for a common purpose. The field research was conducted at a region of State of Minas Gerais, Brazil, where a group of 13 organizations that fit the profile described above, joined up to work jointly, facilitating the environment for local development. The region is between those with the lowest incomes in Brazil. The objective of this study was to verifry what extent the practices implemented by the organizations context (the municipality in question has population of less than 40.000 inhabitants), are contributing to the formation and / or strengthening of a local scene of more opportunities that compete for the quality of life of the population. To meet this goal were interviewd 52 citizens between representatives of organizations, the government, civil society and citizens directly benefit from the Sustainable Araçuaí iniciative, using the semi-structured interview. The result has been the relationship between partnerships determining factors, facilitators and restrictive labour, structured on a conceptual map, and the perception of the impact that these actions have caused coordinates the council from the perspective of the interviewees

Arranjo produtivo local: o caso de São João Del Rei-MG

O objetivo dessa dissertação foi investigar o processo de formação do Arranjo Produtivo Local (APL) de estanho em São João del-Rei - A7 Estanho, particularizando suas contribuições para o desenvolvimento local do município. O trabalho foi conduzido mediante uma discussão teórica sobre a situação das micro e pequenas empresas no Brasil, sobre a importância econômica e social dos arranjos produtivos locais, seus impactos no desenvolvimento regional e/ou local, principalmente de municípios sem infra-estrutura para atrair grandes empresas, e sobre políticas públicas que estão em andamento e que se voltam para o fomento desse tipo de aglomerado. Foram realizadas cerca de quatorze entrevistas no município de São João del-Rei: seis integrantes da Associação, uma funcionária, dois representantes das principais instituições parceiras, um representante do governo local e quatro membros da sociedade civil, que possuíam informações relevantes sobre a A7. O método empregado no tratamento dos dados foi a análise de conteúdo. Como resultados, no que diz respeito à análise dos programas que deram origem e/ou sustentação ao aglomerado, verificou-se que dois programas foram mais contundentes em suas contribuições à Associação: o Programa Empreender, da Federaminas, que permitiu a união dos empresários em torno de um objetivo comum, e o Projeto Via Design, do Sebrae, que possibilitou uma série de vantagens ao grupo, solidificando-o no mercado. No que se refere à participação dos diversos atores (membros da A7, poder público, instituições parceiras, sociedade civil) na construção do APL, pode-se perceber que o nível de atuação e comprometimento variava de acordo com as motivações pessoais, cargos ou funções formais exercidas e grau de relacionamento com a Associação. As contribuições ao desenvolvimento local do município, geradas pelo arranjo produtivo, foram enumeradas como geração de emprego e renda, ainda de forma incipiente, mas com possibilidades de crescimento futuro, e divulgação do turismo e cultura sãojoanense.

Educação escolar e saúde indígena: uma análise comparativa das políticas nos níveis federal e local

Este trabalho apresenta um estudo sobre as políticas de educação escolar e saúde indígena no Brasil, buscando verificar a presença das tendências de modificação observadas nas políticas sociais do país, a partir das décadas de 1980 e 1990: descentralização das políticas para as esferas subnacionais de governo; criação de mecanismos de participação da sociedade civil nos processos decisórios; estabelecimento de parcerias com instituições privadas para a provisão de serviços públicos; institucionalização de canais de controle; alteração no conteúdo das políticas e ampliação de seu alcance. O estudo foi realizado a partir de uma análise comparativa das duas políticas no nível federal e no nível local de governo. A análise no nível local foi realizada a partir do estudo de caso do Parque Indígena do Xingu. Buscou-se verificar, na trajetória das políticas, a influência dos fatores relacionados aos processos de Redemocratização e Reforma do Estado, das dinâmicas próprias das áreas de saúde e educação, da questão indígena e da agenda estatal indigenista. A partir da análise, verificamos, no nível federal, um avanço na legislação de ambos os campos, comparado com os princípios existentes antes da Constituição Federal de 1988. No que se refere à legislação, a educação escolar indígena apresenta-se mais consolidada quando comparada à saúde que ainda apresenta muitas indefinições. No Parque Indígena do Xingu percebemos uma inflexão nas duas políticas, a partir da década de 1990, que passam a buscar um crescente protagonismo indígena e a valorização de uma abordagem intercultural. No Xingu estes avanços foram resultado, sobretudo, da iniciativa das comunidades indígenas da região, em parceria com a Universidade Federal de São Paulo, na área da saúde, e com o Instituto Socioambiental, na área da educação, e com recursos, a principio, de fundações internacionais.

Three essays on local demand for public services

Local provision of public services has the positive effect of increasing the efficiency because each locality has its idiosyncrasies that determine a particular demand for public services. This dissertation addresses different aspects of the local demand for public goods and services and their relationship with political incentives. The text is divided in three essays. The first essay aims to test the existence of yardstick competition in education spending using panel data from Brazilian municipalities. The essay estimates two-regime spatial Durbin models with time and spatial fixed effects using maximum likelihood, where the regimes represent different electoral and educational accountability institutional settings. First, it is investigated whether the lame duck incumbents tend to engage in less strategic interaction as a result of the impossibility of reelection, which lowers the incentives for them to signal their type (good or bad) to the voters by mimicking their neighbors’ expenditures. Additionally, it is evaluated whether the lack of electorate support faced by the minority governments causes the incumbents to mimic the neighbors’ spending to a greater extent to increase their odds of reelection. Next, the essay estimates the effects of the institutional change introduced by the disclosure on April 2007 of the Basic Education Development Index (known as IDEB) and its goals on the strategic interaction at the municipality level. This institutional change potentially increased the incentives for incumbents to follow the national best practices in an attempt to signal their type to voters, thus reducing the importance of local information spillover. The same model is also tested using school inputs that are believed to improve students’ performance in place of education spending. The results show evidence for yardstick competition in education spending. Spatial auto-correlation is lower among the lame ducks and higher among the incumbents with minority support (a smaller vote margin). In addition, the institutional change introduced by the IDEB reduced the spatial interaction in education spending and input-setting, thus diminishing the importance of local information spillover. The second essay investigates the role played by the geographic distance between the poor and non-poor in the local demand for income redistribution. In particular, the study provides an empirical test of the geographically limited altruism model proposed in Pauly (1973), incorporating the possibility of participation costs associated with the provision of transfers (Van de Wale, 1998). First, the discussion is motivated by allowing for an “iceberg cost” of participation in the programs for the poor individuals in Pauly’s original model. Next, using data from the 2000 Brazilian Census and a panel of municipalities based on the National Household Sample Survey (PNAD) from 2001 to 2007, all the distance-related explanatory variables indicate that an increased proximity between poor and non-poor is associated with better targeting of the programs (demand for redistribution). For instance, a 1-hour increase in the time spent commuting by the poor reduces the targeting by 3.158 percentage points. This result is similar to that of Ashworth, Heyndels and Smolders (2002) but is definitely not due to the program leakages. To empirically disentangle participation costs and spatially restricted altruism effects, an additional test is conducted using unique panel data based on the 2004 and 2006 PNAD, which assess the number of benefits and the average benefit value received by beneficiaries. The estimates suggest that both cost and altruism play important roles in targeting determination in Brazil, and thus, in the determination of the demand for redistribution. Lastly, the results indicate that ‘size matters’; i.e., the budget for redistribution has a positive impact on targeting. The third essay aims to empirically test the validity of the median voter model for the Brazilian case. Information on municipalities are obtained from the Population Census and the Brazilian Supreme Electoral Court for the year 2000. First, the median voter demand for local public services is estimated. The bundles of services offered by reelection candidates are identified as the expenditures realized during incumbents’ first term in office. The assumption of perfect information of candidates concerning the median demand is relaxed and a weaker hypothesis, of rational expectation, is imposed. Thus, incumbents make mistakes about the median demand that are referred to as misperception errors. Thus, at a given point in time, incumbents can provide a bundle (given by the amount of expenditures per capita) that differs from median voter’s demand for public services by a multiplicative error term, which is included in the residuals of the demand equation. Next, it is estimated the impact of the module of this misperception error on the electoral performance of incumbents using a selection models. The result suggests that the median voter model is valid for the case of Brazilian municipalities.

Gestão social das políticas públicas de desenvolvimento local: uma análise sobre a participação do Sindicato dos Metalúrgicos no Consórcio Intermunicipal do ABC

O estudo discute as relações entre a participação política da sociedade civil e as políticas públicas no nível subnacional de governo. A pesquisa trata mais especificamente da relação entre a participação sindicalismo nas políticas públicas. Com isso, procura-se pensar os diversos sentidos e significados da participação do sindicato dos Metalúrgicos do ABC nas políticas públicas. O estudo encontra-se inscrito no contexto das pesquisas qualitativas, enfocando a importância da fala.

Statistical modelling of extreme rainfall in Madeira Island

Extreme rainfall events have triggered a significant number of flash floods in Madeira Island along its past and recent history. Madeira is a volcanic island where the spatial rainfall distribution is strongly affected by its rugged topography. In this thesis, annual maximum of daily rainfall data from 25 rain gauge stations located in Madeira Island were modelled by the generalised extreme value distribution. Also, the hypothesis of a Gumbel distribution was tested by two methods and the existence of a linear trend in both distributions parameters was analysed. Estimates for the 50– and 100–year return levels were also obtained. Still in an univariate context, the assumption that a distribution function belongs to the domain of attraction of an extreme value distribution for monthly maximum rainfall data was tested for the rainy season. The available data was then analysed in order to find the most suitable domain of attraction for the sampled distribution. In a different approach, a search for thresholds was also performed for daily rainfall values through a graphical analysis. In a multivariate context, a study was made on the dependence between extreme rainfall values from the considered stations based on Kendall’s τ measure. This study suggests the influence of factors such as altitude, slope orientation, distance between stations and their proximity of the sea on the spatial distribution of extreme rainfall. Groups of three pairwise associated stations were also obtained and an adjustment was made to a family of extreme value copulas involving the Marshall–Olkin family, whose parameters can be written as a function of Kendall’s τ association measures of the obtained pairs.

Abundância das formas imaturas de Psaroniocompsa incrustata ( Lutz, 1910) (Diptera: Simuliidae) em um criadouro natural no rio Pium/RN, e sua fauna associada

The species psaroniocompsa incrustata (Lutz, 1910) was studied in relation to its abundance in different and seasonal periods, the physico-chemical of the breending ground and the fauna predation added to the immature of the species. The study was developed during eight months, from April to July, 2005 (rainy season) and from October, 2005 to January, 2006 (drought season), in one natural breending ground situated in the Pium river, that is part of the hydrographical basin of the Pirangi river in Rio Grande do Norte. The immature of Simuliidae were collected manually in vegetal substrate. At the same place, it was made one sampling of the associated fauna using Suber collectors and the measurement of the environment variants. It was also made one analysis of the stomach content of possible enemies of the simulídeos, to observe the predation of the associated fauna. It was collected 7.713 samples, all from de species P. Incrustata, it was observed a bigger abundance in the drought season, and the entomologic fauna associated totalizing 20.1314 species, distributed in the kinds: Diptera, Ephemeroptera, Odonata, Trichoptera, e Hemiptera, with a bigger representativity of Dipteros. The analysis of the stomach content of the species from the families Libellulidae and Hydropsychidae showed the presence of the simulídeos in only 4% of the material analysed, therefore it was not confirmed the presence of one efficient biological control of the simulídeos in this breending ground

Caracterização batimétrica e fisicooceanográfica do canal de acesso ao porto de Cabedelo/PB: uma análise ambiental ao derrame de óleo

The State of Paraíba is one of the most dynamic states of Brazil, strategically located in the northeast, is notable for the excellent potential for integration of different transportation modes forming the states of Rio Grande do Norte, Pernambuco and Alagoas. The dynamic that occurs with port activity causes changes in the space where it is installed. And the elements of this space are always more than suffering direct or indirect influences as the flow in the port is expanded. Therefore, this region became subject to the accidental spillage of oil, because it presents a heavy traffic of ships of various sizes that can run aground or collide with oil causing accidental events. The study of geomorphological and sedimentological compositions of seafloor becomes important as more is known about the relationships between these parameters and associated fauna, and can identify their preferred habitats. The database background, acoustically collected along the proposed study area, is a wealth of information, which were duly examined, cataloged and made available. Such information can serve as an important tool, providing a geomorphological survey of the sedimentary area studied, and come to subsidize, in a flexible, future decision making. With the study area Port of Cabedelo, Paraíba - Brazil, this research aimed to evaluate the influence of the tidal surface and background in modeling the seabed, including the acquisition of information about the location of submerged rocky bodies and the depth of these bodies may turn out to be natural traps for the trapping of oil in case of leaks, and obtain the relationship between types of bed and the hydrodynamic conditions present in the region. In this context, for this study were collected bathymetric data (depth) and physical oceanographic (height of water column, water temperature, intensity and direction of currents, waves and turbidity), meteorological (rainfall, air temperature, humidity, winds and barometric pressure) of the access channel to the Port of Cabedelo / PB and its basin evolution (where the cruise ships dock), and includes tools of remote sensing (Landsat 7 ETM +, 2001), so that images and the results are integrated into Geographic Information Systems and used in the elaboration of measures aimed at environmental protection areas under the influence of this scale facilities, serving as a grant to prepare a contingency plan in case of oil spills in the region. The main findings highlight the techniques of using hydroacoustic data acquisition together bathymetric surveys of high and low frequency. From there, five were prepared in bathymetric pattern of Directorate of Hydrography and Navigation - DHN, with the depth in meters, on a scale of 1:2500 (Channel and Basin Evolution of Access to Port of Cabedelo), where there is a large extent possible beachrocks that hinder the movement of vessels in the port area, which can cause collisions, running aground and leaking oil. From the scatter diagram of the vectors of currents, it can be seen as the tidal stream and undergoes a channeling effect caused by the bidirectional effect of the tide (ebb and flood) in the basin of the Port of Cabedelo evolution in NW-direction SE and the highest speed of the currents occurs at low tide. The characterization weather for the period from 28/02 to 04/07/2010 values was within the expected average for the region of study. The multidisciplinary integration of products (digital maps and remote sensing images), proved to be efficient for the characterization of underwater geomorphological study area, reaching the aim to discriminate and enhance submerged structures, previously not visible in the images

Aerial line transect survey to estimate abundance of marsh deer (Blastocerus dichotomus) (Illiger, 1815)

A população de cervo-do-pantanal (Blastocerus dichotomus) está drasticamente reduzida no Brasil. O nosso objetivo foi o de estimar a abundância do cervo-do-pantanal na bacia do Rio Paraná e discutir a metodologia aplicada. Os resultados darão suporte para uma análise do impacto do enchimento da represa de Porto Primavera sobre essa população. Sessenta e nove animais foram registrados através de sobrevôo utilizando-se a metodologia de transecção linear com amostragem das distâncias. Os dados não corrigidos resultaram em uma densidade estimada de 0,0035ind/ha e uma população de 636 indivíduos. A correção de g para os animais que não foram vistos apresentou uma densidade de 0,0049 ind/ha e uma abundância de 896 (CV=0,27) indivíduos. A metodologia foi aplicada com sucesso na estimativa de cervo-do-pantanal. Esse resultado é importante para avaliarmos a população do cervo-do-pantanal na área e para futuramente analisarmos o impacto do enchimento da represa.