Photoisomerization for a model protonated Schiff base in solution: Sloped/peaked conical intersection perspective

The topographical character of conical intersections (CIs)-either sloped or peaked-has played a fundamental and important role in the discussion of the efficiency of CIs as photochemical "funnels." Here this perspective is employed in connection with a recent study of a model protonated Schiff base (PSB) cis to trans photoisomerization in solution [Malhado et al., J. Phys. Chem. A 115, 3720 (2011)]. In that study, the calculated reduced photochemical quantum yield for the successful production of trans product versus cis reactant in acetonitrile solvent compared to water was interpreted in terms of a dynamical solvent effect related to the dominance, for the acetonitrile case, of S-1 to S-0 nonadiabatic transitions prior to the reaching the seam of CIs. The solvent influence on the quantum yield is here re-examined in the sloped/peaked CI topographical perspective via conversion of the model's two PSB internal coordinates and a nonequilibrium solvent coordinate into an effective branching space description, which is then used to re-analyze the generalized Langevin equation/surface hopping results. The present study supports the original interpretation and enriches it in terms of topographical detail. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754505]

Cartographic notes on the work in the Family Health Strategy: relationships between workers and the population

The objective of this intervention study was to map instituted and instituting movements present in the work of the Family Health Strategy in the development of their care practices. The theoretical framework is based on institutional analysis, using the schizoanalytic approach. Group meetings were carried out with the staff to discuss how they provided collective care in continuing health education. The study subjects were professionals from the team and students who were engaged in academic activity in the service. The average attendance was twelve people per meeting, and there were a total of eight meetings from March to July 2010. Data were grouped into two immanent strata: the relationships of the team and the relationship with clients. The strata point to the intersection of education and legal institutions and the social and technical division of labor. Collective thinking in groups appeared to be effective in denaturalizing established processes and interrogating places, knowledge and practices.

Positive fluid balance is associated with reduced survival in critically ill patients with cancer

Background There are no studies that describe the impact of the cumulative fluid balance on the outcomes of cancer patients admitted to intensive care units ICUs. The aim of our study was to evaluate the relationship between fluid balance and clinical outcomes in these patients. Method One hundred twenty-two cancer patients were prospectively evaluated for survival during a 30-day period. Univariate (Chi-square, t-test, MannWhitney) and multiple logistic regression analyses were used to identify the admission parameters associated with mortality. Results The mean cumulative fluid balance was significantly higher in non-survivors than in survivors [1675?ml/24?h (4712921) vs. 887?ml/24?h (104557), P?=?0.017]. We used the area under the curve and the intersection of the sensibility and specificity curves to define a cumulative fluid balance value of 1100?ml/24?h. This value was used in the univariate model. In the multivariate model, the following variables were significantly associated with mortality in cancer patients: the Acute Physiology and Chronic Health Evaluation II score at admission [Odds ratio (OR) 1.15; 95% confidence interval (CI) (1.051.26), P?=?0.003], the Lung Injury Score at admission [OR 2.23; 95% CI (1.293.87), P?=?0.004] and a positive fluid balance higher than 1100?ml/24?h at ICU [OR 5.14; 95% CI (1.4518.24), P?=?0.011]. Conclusion A cumulative positive fluid balance higher than 1100?ml/24?h was independently associated with mortality in patients with cancer. These findings highlight the importance of improving the evaluation of these patients' volemic state and indicate that defined goals should be used to guide fluid therapy.

On the Mechanisms of Triplet Excited State Population in 8-Azaadenine

The photophysics of 8-azaadenine (8-AA) has been studied with the CASPT2//CASSCF protocol and ANO-L double-zeta basis sets. Stationary equilibrium structures, surface crossings, minimum energy paths, and linear interpolations have been used to study possible mechanisms to populate the lowest triplet state, T-1 (3)(pi pi*), capable of sensitizing molecular oxygen. Our results show that two main mechanisms can occur after photoexcitation to the S-2 (1)(pi pi*) state. The first one is through the S-2/S-1 conical intersection (((1)pi pi*/(1)n pi*)(Cl)), leading to the S-1 ((1)n pi*) state minimum, (S-1 ((1)n pi*))(min), where a singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), is accessible. The second one starts with the ((1)pi pi*/(3)n pi*)(STC) at the (S-2((1)pi pi*))(min), from which the system can evolve to the (T-2 ((3)n pi*))(min), with subsequent population of the T-1 excited electronic state, due to the ((3)n pi*/(3)pi pi*)(Cl) conical intersection.

Bioethical Aspects Across Medicine: The Care of Cardiovascular Diseases in Brazil

Bioethics applied to medicine extrapolates the traditional medical concepts of non-maleficence (primum non nocere) and beneficence (bonum facere) and regards to justice, autonomy, equity, protection, compassion and humanization, not considering people just like patients, but understanding the complex existence of each single person. Worldwide, the morbidity and mortality indices regarding to diseases of heart and blood vessels became progressively grater. For countries in development, like Brazil, these numbers are even more expressive and this increase trend seems to be caused by wider exposition of population to some risk factors. This article broaches an intersection between bioethics and medicine, focusing the reality of cardiovascular diseases in Brazil and the necessity of doctors to base their behavior in bioethical paradigms.

The SB-index and the HSB-index: efficient indices for spatial data warehouses

Spatial data warehouses (SDWs) allow for spatial analysis together with analytical multidimensional queries over huge volumes of data. The challenge is to retrieve data related to ad hoc spatial query windows according to spatial predicates, avoiding the high cost of joining large tables. Therefore, mechanisms to provide efficient query processing over SDWs are essential. In this paper, we propose two efficient indices for SDW: the SB-index and the HSB-index. The proposed indices share the following characteristics. They enable multidimensional queries with spatial predicate for SDW and also support predefined spatial hierarchies. Furthermore, they compute the spatial predicate and transform it into a conventional one, which can be evaluated together with other conventional predicates by accessing a star-join Bitmap index. While the SB-index has a sequential data structure, the HSB-index uses a hierarchical data structure to enable spatial objects clustering and a specialized buffer-pool to decrease the number of disk accesses. The advantages of the SB-index and the HSB-index over the DBMS resources for SDW indexing (i.e. star-join computation and materialized views) were investigated through performance tests, which issued roll-up operations extended with containment and intersection range queries. The performance results showed that improvements ranged from 68% up to 99% over both the star-join computation and the materialized view. Furthermore, the proposed indices proved to be very compact, adding only less than 1% to the storage requirements. Therefore, both the SB-index and the HSB-index are excellent choices for SDW indexing. Choosing between the SB-index and the HSB-index mainly depends on the query selectivity of spatial predicates. While low query selectivity benefits the HSB-index, the SB-index provides better performance for higher query selectivity.

Counting singularities via fitting ideals

The stable singularities of differential map germs constitute the main source of studying the geometric and topological behavior of these maps. In particular, one interesting problem is to find formulae which allow us to count the isolated stable singularities which appear in the discriminant of a stable deformation of a finitely determined map germ. Mond and Pellikaan showed how the Fitting ideals are related to such singularities and obtain a formula to count the number of ordinary triple points in map germs from C-2 to C-3, in terms of the Fitting ideals associated with the discriminant. In this article we consider map germs from (Cn+m, 0) to (C-m, 0), and obtain results to count the number of isolated singularities by means of the dimension of some associated algebras to the Fitting ideals. First in Corollary 4.5 we provide a way to compute the total sum of these singularities. In Proposition 4.9, for m = 3 we show how to compute the number of ordinary triple points. In Corollary 4.10 and with f of co-rank one, we show a way to compute the number of points formed by the intersection between a germ of a cuspidal edge and a germ of a plane. Furthermore, we show in some examples how to calculate the number of isolated singularities using these results.

Periódicos de Ciência da Informação nas bases de dados internacionais

PO artigo demonstra as interações entre algumas bases de dados internacionais na disponibilização de periódicos da área de Ciência da Informação. Para isso, foram investigadas seis bases de dados com acesso a texto completo dentro da área de Ciência da Informação. Foram elas: Web of Science, Scopus, Library, Information Science & Technology Abstracts, Information Science & Technology Abstracts, Library Literature Information Science – full text e Library Information Science Abstract. No desenvolvimento da pesquisa foram utilizados conceitos, princípios e equações da ‘teoria ingênua dos conjuntos’, o que permitiu observar as bases de dados como conjuntos compostos por elementos, aqui considerados os títulos de periódicos, bem como conferir consistência aos resultados. A análise dos dados foi dividida em três etapas, a saber: a) a primeira priorizou o cruzamento entre as duas maiores bases de dados utilizadas para levantamento bibliográfico (Web of Science e Scopus), seguido do cruzamento com a mais utilizada na Ciência da Informação, a Library and Information Science Abstracts; b) a segunda etapa tratou somente do cruzamento das bases especialistas da área; c) a terceira e última etapa tratou da interseção de todas as bases de dados do estudo. O resultado mostra que 10 títulos de periódicos constituem a interseção dos seis conjuntos de bases de dados. Foi possível identificar, também, o número de periódicos disponibilizados exclusivamente por uma base de dados, demonstrando que as necessidades de pesquisas bibliográficas exaustivas passam, obrigatoriamente, pelo levantamento em todas as bases de dados aqui elencadas.

80 anos do Manifesto dos Pioneiros da Educação Nova: questões para debate

O artigo, produzido no âmbito das comemorações dos 80 anos de publicação do Manifesto dos Pioneiros da Educação Nova, interroga-se sobre a atualidade dessa carta. Para tanto, explora as condições históricas de emergência do documento, os significados atribuídos à Escola Nova no Brasil na década de 1930 e as contendas ocorridas na arena educacional no período. Além disso, discorre sobre as especificidades do movimento escolanovista brasileiro, procurando demonstrar que a Escola Nova constituiu-se no país como uma fórmula, com significados múltiplos e distintas apropriações produzidas no entrelaçamento de três vertentes: a pedagógica, a ideológica e a política. No que tange ao primeiro aspecto, a indefinição das fronteiras conceituais permitiu que a expressão Escola Nova aglutinasse diferentes educadores, católicos e liberais, em torno de princípios pedagógicos do ensino ativo. No segundo caso, a fórmula ofereceu-se como meio para a transformação da sociedade, servindo às finalidades divergentes dos grupos em litígio. Já na terceira acepção, tornou-se bandeira política, sendo capturada como signo de renovação do sistema educacional pelo Manifesto e por seus signatários. Assim, o documento emergiu como parte do jogo político pela disputa do controle do Estado e de suas dinâmicas, e, portanto, como elemento de coesão de uma frente de educadores que, a despeito de suas diferenças, articulava-se em torno de alguns objetivos comuns, como laicidade, gratuidade e obrigatoriedade da educação. Ademais, ele também foi representante de um grupo de intelectuais que abraçava um mesmo projeto de nação, ainda que com divergências internas.