Discrete cyanide-bridged mixed-valence Co/Fe complexes: Outer-sphere redox behaviour

The outer-sphere redox behaviour of a series of [LnCoIII-NCFeII(CN)(5)](-) (L-n = n-membered pentadentate aza-macrocycle) complexes have been studied as a function of pH and oxidising agent. All the dinuclear complexes show a double protonation process at pH approximate to 2 that produces a shift in their UV/Vis spectra. Oxidation of the different non-protonated and diprotonated complexes has been carried out with peroxodisulfate, and of the non-protonated complexes also with trisoxalatocobaltate(III). The results are in agreement with predictions from the Marcus theory. The oxidation of [Fe(phen)(3)](3+) and [IrCl6](2-) is too fast to be measured, although for the latter the transient observation of the process has been achieved at pH = 0. The study of the kinetics of the outer-sphere redox process, with the S2O82- and [Co(ox)(3)](3-) oxidants, has been carried out as a function of pH, temperature, and pressure. As a whole, the values found for the activation volumes, entropies, and enthalpies are in the following margins, for the diprotonated and non-protonated dinuclear complexes, respectively: DeltaV(not equal) from 11 to 13 and 15 to 20 cm(3) mol(-1); DeltaS(not equal) from 110 to 30 and -60 to -90 J K-1 mol(-1); DeltaH(not equal) from 115 to 80 and 50 to 65 kJ.mol(-1). The thermal activation parameters are clearly dominated by the electrostriction occurring on outer-sphere precursor formation, while the trends found for the values of the volume of activation indicate an important degree of tuning due to the charge distribution during the electron transfer process. The special arrangement on the amine ligands in the isomer trans[(L14CoNCFeII)-N-III(CN)(5)](-) accounts for important differences in solvent-assisted hydrogen bonding occurring within the outer-sphere redox process, as has been established in redox reactions of similar compounds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

A mudan??a de pol??tica na crise do Estado de Bem Estar Social: uma an??lise comparada

O artigo faz uma identifica????o das caracter??sticas da policy change que vem sendo assumidas nos ??ltimos anos, nos diversos setores da interven????o p??blica, com base no exame das mudan??as das pol??ticas nas principais democracias contempor??neas integrantes da OCDE. Focaliza a tend??ncia, que parece ser mais real e de longo prazo, expressa na passagem do Estado social para o Estado gerencial.

Variação na dieta da tartaruga verde, Chelonia mydas, e o impacto da ingestão de lixo ao longo da costa brasileira

Neste trabalho nós estudamos a dieta da tartaruga verde, Chelonia mydas, e os fatores envolvidos na variação de sua ecologia alimentar. Avaliamos também o impacto da ingestão de lixo, e os fatores que podem explicar a elevada ingestão destes resíduos entre os animais marinhos. No estudo da ecologia alimentar, nós avaliamos mais de 400 indivíduos, entre dados originais e da literatura, distribuídos ao longo de um gradiente latitudinal e diversos ambientes. As tartarugas se alimentaram majoritariamente de macroalgas, porém apresentaram uma grande plasticidade alimentar, tanto em relação à estratégia de forrageamento quanto à dieta. Nas regiões mais frias e com menor disponibilidade de algas, as tartarugas mudaram de uma dieta herbívora, para uma dieta baseada em matéria animal. Esta mudança de dieta acarretou também em uma mudança de estratégia de forrageamento, saindo da alimentação bentônica para uma alimentação pelágica. Estratégia esta que também foi encontrada nas áreas estuarinas. A plasticidade alimentar se deve à interação de fatores intrínsecos (restrições fisiológicas) e extrínsecos (regionais e locais). As diferenças nas estratégias de forragenamento acarretam também em diferenças na exposição a ameaças. Um exemplo disso é a ingestão de lixo, que apesar de ter sido registrada em mais de 70% das tartarugas (N = 265), representou uma ameaça maior aos animais com estratégia de forrageamento pelágica. O plástico foi o material mais ingerido, tendo como principal fonte itens relacionados à alimentação e sacolas plásticas. O estudo também mostrou que uma quantidade pequena de lixo (0,5 g) é suficiente para causar a morte. Este resultado revelou que o potencial de letalidade por ingestão de lixo é muito maior que a mortalidade observada. A verdadeira ameaça da ingestão de lixo está sendo mascarada pela elevada mortalidade relacionada às atividades pesqueiras. A ingestão de lixo é normalmente atribuída à confusão de um item alimentar específico com o resíduo, como águas-vivas e sacolas plásticas. Porém, nós mostramos que se trata de uma questão mais ampla, e usamos a tartaruga verde, aves marinhas e peixes para ressaltar a importância de outros fatores como: abundância do lixo no ambiente, estratégia de forrageamento, capacidade de detecção do resíduo e amplitude da dieta. Nós acreditamos que a ingestão de lixo ocorre devido a uma armadilha evolutiva muito mais ampla do que a previamente sugerida, e que deve afetar muito mais espécies que as que foram até hoje reportadas. Desarmar esta armadilha será particularmente difícil devido ao contínuo e crescente despejo de plástico no ambiente marinho e sua alta persistência no ambiente.

Security issues during Lula's administration: from the reactive to the assertive approach

Brazil's security agenda during Lula's administration was not homogeneous through the two mandates: the first tenure (2002-2006) revealed a reactive approach towards security topics, while the second one (2006-2010) was more assertive. More specifically, the shift occurred in terms of both its geographical scope - once it incorporated global issues in a more systematic way -, and instruments through which the security agenda was exercised, given the multilateral initiative of Unasur's CDS

Architectural prototyping: from CCS to .Net

Over the last decade, software architecture emerged as a critical issue in Software Engineering. This encompassed a shift from traditional programming towards software development based on the deployment and assembly of independent components. The specification of both the overall systems structure and the interaction patterns between their components became a major concern for the working developer. Although a number of formalisms to express behaviour and to supply the indispensable calculational power to reason about designs, are available, the task of deriving architectural designs on top of popular component platforms has remained largely informal. This paper introduces a systematic approach to derive, from CCS behavioural specifications the corresponding architectural skeletons in the Microsoft .Net framework, in the form of executable C and Cω code. The prototyping process is fully supported by a specific tool developed in Haskell

Collecting system percutaneous access using real-time tracking sensors: first pig model in vivo experience

Purpose: Precise needle puncture of the renal collecting system is an essential but challenging step for successful percutaneous nephrolithotomy. We evaluated the efficiency of a new real-time electromagnetic tracking system for in vivo kidney puncture. Materials and Methods: Six anesthetized female pigs underwent ureterorenoscopy to place a catheter with an electromagnetic tracking sensor into the desired puncture site and ascertain puncture success. A tracked needle with a similar electromagnetic tracking sensor was subsequently navigated into the sensor in the catheter. Four punctures were performed by each of 2 surgeons in each pig, including 1 each in the kidney, middle ureter, and right and left sides. Outcome measurements were the number of attempts and the time needed to evaluate the virtual trajectory and perform percutaneous puncture. Results: A total of 24 punctures were easily performed without complication. Surgeons required more time to evaluate the trajectory during ureteral than kidney puncture (median 15 seconds, range 14 to 18 vs 13, range 11 to 16, p ¼ 0.1). Median renal and ureteral puncture time was 19 (range 14 to 45) and 51 seconds (range 45 to 67), respectively (p ¼ 0.003). Two attempts were needed to achieve a successful ureteral puncture. The technique requires the presence of a renal stone for testing. Conclusions: The proposed electromagnetic tracking solution for renal collecting system puncture proved to be highly accurate, simple and quick. This method might represent a paradigm shift in percutaneous kidney access techniques

Prototyping Behavioural Specifications in the.NET framework

Over the last decade, software architecture emerged as a critical design step in Software Engineering. This encompassed a shift from traditional programming towards the deployment and assembly of independent components. The specification of the overall system structure, on the one hand, and of the interactions patterns between its components, on the other, became a major concern for the working developer. Although a number of formalisms to express behaviour and supply the indispensable calculational power to reason about designs, are available, the task of deriving architectural designs on top of popular component platforms has remained largely informal. This paper introduces a systematic approach to derive, from behavioural specifications written in Ccs, the corresponding architectural skeletons in the Microsoft .Net framework in the form of executable C] code. Such prototyping process is automated by means of a specific tool developed in Haskell

A Representação de Personagens Virtuais: Como a Tecnologia Obriga à Criação de Estilos e Estéticas Interdisciplinares na Animação Contemporânea

The evolution of computer animation represents one of the most relevant andrevolutionary aspects in the rise of contemporary digital visual culture (Darlew,2000), in particular, phenomena such as cinema “spectacular “ (Ibidem) and videogames. This article analyzes the characteristics of this “culture of simulation” (Turkle, 1995:20) relating the multidisciplinary and spectrum of technical and stylistic choices to the dimension of virtual characters acting. The result of these hybrid mixtures and computerized human motion capture techniques - called virtual cinema, universal capture, motion capture, etc. - cosists mainly on the sophistication of “rotoscoping”, as a new interpretation and appropriation of the captured image. This human motion capture technology, used largely by cinema and digital games, is one of the reasons why the authenticity of the animation is sometimes questioned. It is in the fi eld of 3D computer animation visual that this change is more signifi cant, appearing regularly innovative techniques of image manipulation and “hyper-cinema” (Lamarre, 2006: 31) character’s control with deeper sense of emotions. This shift in the culture that Manovich (2006: 27) calls “photo-GRAPHICS” - and Mulvey (2007) argue that creates a new form of possessive relationship with the viewer, in that it can analyze in detail the image, it can acquire it and modify it - is one of the most important aspects in the rise of Cubbit’s (2007) “cinema of attraction”. This article delves intrinsically into the analyze of virtual character animation — particularly in the fi eld of 3D computer animation and human digital acting.

Impactos do crescimento da produção de cana-de-açúcar na agricultura dos oito maiores estados produtores

Nesta pesquisa, buscou-se analisar o processo de substituição de culturas, ocorrido nos principais estados produtores de cana-de-açúcar, no período de 2000 a 2010, utilizando o modelo shift-share. Os estados de Alagoas, Goiás, Mato Grosso, Mato Grosso do Sul, Minas Gerais, Paraná, Pernambuco e São Paulo foram considerados na análise. De modo geral, os resultados mostram que a agricultura desses estados foi afetada pela forte expansão da área cultivada com cana-de-açúcar e com soja. Esse crescimento baseou-se, em parte, na substituição de outros produtos, principalmente arroz, feijão e milho, além de café, algodão e laranja. Apesar disso, os ganhos de produtividade contribuíram para reduzir, ou mesmo superar, os efeitos da perda de área dos produtos substituídos. Porém, a agricultura dos estados mais afetados pelo crescimento da participação da cana-de-açúcar e da soja tornou-se menos diversificada e, portanto, mais exposta a eventuais crises no mercado dos produtos em que passou a se basear.

Collecting system percutaneous access using real-time tracking sensors: first pig model in vivo experience

Purpose: Precise needle puncture of the renal collecting system is an essential but challenging step for successful percutaneous nephrolithotomy. We evaluated the efficiency of a new real-time electromagnetic tracking system for in vivo kidney puncture. Materials and Methods: Six anesthetized female pigs underwent ureterorenoscopy to place a catheter with an electromagnetic tracking sensor into the desired puncture site and ascertain puncture success. A tracked needle with a similar electromagnetic tracking sensor was subsequently navigated into the sensor in the catheter. Four punctures were performed by each of 2 surgeons in each pig, including 1 each in the kidney, middle ureter, and right and left sides. Outcome measurements were the number of attempts and the time needed to evaluate the virtual trajectory and perform percutaneous puncture. Results: A total of 24 punctures were easily performed without complication. Surgeons required more time to evaluate the trajectory during ureteral than kidney puncture (median 15 seconds, range 14 to 18 vs 13, range 11 to 16, p ¼ 0.1). Median renal and ureteral puncture time was 19 (range 14 to 45) and 51 seconds (range 45 to 67), respectively (p ¼ 0.003). Two attempts were needed to achieve a successful ureteral puncture. The technique requires the presence of a renal stone for testing. Conclusions: The proposed electromagnetic tracking solution for renal collecting system puncture proved to be highly accurate, simple and quick. This method might represent a paradigm shift in percutaneous kidney access techniques.

O radiojornalismo em Portugal

A presente dissertação de mestrado incide sobre o radiojornalismo português. Para a concretizar foi feito um estudo comparativo entre as três rádios de carácter informativo de Portugal: Antena 1, Rádio Renascença e TSF. No sentido de melhor clarificar esta tese, são analisadas as grelhas de programação do programa da manhã destas estações. Está igualmente patente neste trabalho uma consideração sobre a história destas três emissoras e são evidenciados marcos que representam um verdadeiro e notório contributo para o jornalismo de rádio feito em Portugal. Para tal foi usada uma metodologia em que se fez um levantamento – a cada cinco anos - de todos os programas da manhã desde há trinta anos até hoje, no sentido de compreender as suas evoluções e comparar as diferenças das apostas de cada uma das rádios. As conclusões deste estudo apontam para o facto de as manhãs da rádio serem um período onde as notícias têm grande importância, bem como um período em que se tratam assuntos relativos à sociedade. Na Antena 1 e na TSF a inclusão de programas como “Antena Aberta” ou “Fórum TSF” faz com que a temática da sociedade, que engloba um grande número de temas e assuntos sejam a predominante. Na Rádio Renascença, apesar do seu cariz informativo, o entretenimento tem mais destaque. Uma observação notória foi também o evoluir da programação de 1985 a 2015, onde houve alterações consideráveis, tais como o aumento dos espaços dedicados a notícias e naturalmente assuntos sociais, dado que em 1985 não existia nenhum programa de opinião pública. Estes espaços foram sem dúvida, algo que marcou e fez uma mudança de paradigma no radiojornalismo português.

Photo-induced instability of nanocrystalline silicon TFTs

We examine the instability behavior of nanocrystalline silicon (nc-Si) thin-film transistors (TFTs) in the presence of electrical and optical stress. The change in threshold voltage and sub-threshold slope is more significant under combined bias-and-light stress when compared to bias stress alone. The threshold voltage shift (Delta V-T) after 6 h of bias stress is about 7 times larger in the case with illumination than in the dark. Under bias stress alone, the primary instability mechanism is charge trapping at the semiconductor/insulator interface. In contrast, under combined bias-and-light stress, the prevailing mechanism appears to be the creation of defect states in the channel, and believed to take place in the amorphous phase, where the increase in the electron density induced by electrical bias enhances the non-radiative recombination of photo-excited electron-hole pairs. The results reported here are consistent with observations of photo-induced efficiency degradation in solar cells.

A new sedimentary benchmark for the Deccan Traps volcanism?

The origin of the Cretaceous-Paleogene boundary (KPB) mass extinction is still the center of acrimonious debates by opposing partisans of the bolide impact theory to those who favored a terrestrial origin linked to the Deccan Traps volcanism. Here we apply an original and high-resolution environmental magnetic study of the reference Bidart section, France. Our results show that the KPB is identified by an abrupt positive shift of the magnetic susceptibility (MS), also observed by others at the KPB elsewhere. In addition, an anomalous interval of very low MS, carried by an unknown Cl-bearing iron oxide similar to specular hematite, is depicted just below the KPB. Grain-size and morphology of the Cl-iron oxide are typically in the range of hematitic dust currently transported by winds from Sahara to Europe. This discovery is confirmed in the referenced Gubbio section (Italy) suggesting a global scale phenomenon. As a conjecture we suggest an origin by heterogeneous reaction between HCl-rich volcanic gas and liquid-solid aerosols within buoyant atmospheric plumes formed above the newly emitted Deccan flood basalts. Based on this hypothesis, our discovery provides a new benchmark for the Deccan volcanism and witnesses the nature and importance of the related atmospheric change.

Housework, paid work and psychiatric symptoms

OBJECTIVE: To evaluate the hypothesis that work burden, the simultaneous engagement in paid work and unpaid family housework, is a potential risk factor for psychiatric symptoms among women. METHODS: A cross-sectional study was carried out with 460 women randomly selected from a poor area of the city of Salvador, Brazil. Women between 18 to 70 years old, who reported having a paid occupation or were involved in unpaid domestic activities for their families, were eligible. Work burden-related variables were defined as: a) double work shift, i.e., simultaneous engagement in a paid job plus unpaid housework; and b) daily working time. Psychiatric symptoms were collected through a validated questionnaire, the QMPA. RESULTS: Positive, statistically significant associations between high (>7 symptoms) QMPA scores and either double work shift (prevalence ratio -- PR=2.04, 95% confidence interval -- CI: 1.16, 2.29) or more than 10 hours of daily work time (PR=2.29, 95% CI: 1.96, 3.43) were found after adjustment for age, marital status and number of pre-school children. CONCLUSIONS: Major correlates of high QMPA scores are work burden variables. Being married or having pre-school children are also associated with high QMPA scores only when associated with work burden.

Age transition of tuberculosis incidence and mortality in Brazil

OBJECTIVE: Before the Aids pandemic, demographic transition and control programs prompted a shift in the age of incidence of tuberculosis from adults to older people in many countries. The objective of the study is to evaluate this transition in Brazil. METHODS: Tuberculosis incidence and mortality data from the Ministry of Health and population data from the Brazilian Bureau of Statistics were used to calculate age-specific incidence and mortality rates and medians. RESULTS: Among reported cases, the proportion of older people increased from 10.5% to 12% and the median age from 38 to 41 years between the period of 1986 and 1996. The smallest decrease in the incidence rate occurred in the 30--49 and 60+ age groups. The median age of death increased from 53 to 55 years between 1980 and 1996. The general decline in mortality rates from 1986 to 1991 became less evident in the 30+ age group during the period of 1991 to 1996. A direct correlation between age and mortality rates was observed. The largest proportion of bacteriologically unconfirmed cases occurred in older individuals. CONCLUSIONS: The incidence of tuberculosis has begun to shift to the older population. This shift results from the decline in the annual risk of infection as well as the demographic transition. An increase in reactivation tuberculosis in older people is expected, since this population will grow from 5% to 14% of the Brazilian population over the next 50 years. A progressive reduction in HIV-related cases in adults will most likely occur. The difficulty in diagnosing tuberculosis in old age leads to increased mortality.