Copper(II) complexes of tetradentate N2S2 donor sets: synthesis, crystal structure characterization and reactivity

Two mononuclear and one dinuclear copper(II) complexes, containing neutral tetradentate NSSN type ligands, of formulation [Cu-II(L-1)Cl]ClO4 (1), [Cu-II(L-2)Cl]ClO4 (2) and [Cu-2(II)(L-3)(2)Cl-2](ClO4)(2) (3) were synthesized and isolated in pure form [where L-1 = 1,2-bis(2-pyridylmethylthio)ethane, L-2 = 1,3-bis(2-pyridylmethylthio)propane and L-3 = 1,4-bis(2-pyridylmethylthio)butane]. All these green colored copper(II) complexes were characterized by physicochemical and spectroscopic methods. The dinuclear copper(II) complex 3 changed to a colorless dinuclear copper(I) species of formula [Cu-2(1)(L-3)(2)](ClO4)(2),0.5H(2)O (4) in dimethylformamide even in the presence of air at ambient temperature, while complexes I and 2 showed no change under similar conditions. The solid-state structures of complexes 1, 2 and 4 were established by X-ray crystallography. The geometry about the copper in complexes 1 and 2 is trigonal bipyramidal whereas the coordination environment about the copper(I) in dinuclear complex 4 is distorted tetrahedral. (C) 2008 Elsevier Ltd. All rights reserved.

Contextual emergence of mental states from neurodynamics

The emergence of mental states from neural states by partitioning the neural phase space is analyzed in terms of symbolic dynamics. Well-defined mental states provide contexts inducing a criterion of structural stability for the neurodynamics that can be implemented by particular partitions. This leads to distinguished subshifts of finite type that are either cyclic or irreducible. Cyclic shifts correspond to asymptotically stable fixed points or limit tori whereas irreducible shifts are obtained from generating partitions of mixing hyperbolic systems. These stability criteria are applied to the discussion of neural correlates of consiousness, to the definition of macroscopic neural states, and to aspects of the symbol grounding problem. In particular, it is shown that compatible mental descriptions, topologically equivalent to the neurodynamical description, emerge if the partition of the neural phase space is generating. If this is not the case, mental descriptions are incompatible or complementary. Consequences of this result for an integration or unification of cognitive science or psychology, respectively, will be indicated.

On combination of SMOTE and particle swarm optimization based radial basis function classifier for imbalanced problems

The combination of the synthetic minority oversampling technique (SMOTE) and the radial basis function (RBF) classifier is proposed to deal with classification for imbalanced two-class data. In order to enhance the significance of the small and specific region belonging to the positive class in the decision region, the SMOTE is applied to generate synthetic instances for the positive class to balance the training data set. Based on the over-sampled training data, the RBF classifier is constructed by applying the orthogonal forward selection procedure, in which the classifier structure and the parameters of RBF kernels are determined using a particle swarm optimization algorithm based on the criterion of minimizing the leave-one-out misclassification rate. The experimental results on both simulated and real imbalanced data sets are presented to demonstrate the effectiveness of our proposed algorithm.

The anions [(ZrOH(CO3)3)2]6− and [(ZrOH(C2O4)3)2]6−: single crystal X-ray diffraction studies of the complexes guanidinium zirconium carbonate [(C(NH2)3)3ZrOH(CO3)3·H2O]2 and sodium zirconium oxalate Na6(ZrOH(C2O4)3)2·7H2O

The complex [(C(NH2)3)3ZrOH(CO3)3·H2O]2 (A) has been shown by means of a single crystal X-ray diffraction study to contain [C(NH2)3]+ cations and dimeric anions of formulation [(ZrOH(CO3)3)2]6−. The anion is centrosymmetric with each metal being bonded to two bridging OH groups and three chelating CO2−3 ions. The Zr atoms are thus eight coordinate with a dodecahedral environments. The ZrO distances formed by the bridgng OH groups are shorter than those formed through zirconiu carbonate interactions. The non-bonded Zr…Zr distance is 3.47(2) Å. An infrared spectroscopic investigation of A provides data which support the findings of the crystallographic study. Likewise the complex Na6(ZrOH(CO2O4)3)2·7H2O (B) contains the anion [(ZrOH(C2O4)3)2]6−. This anion is structurally related to the anion in A as each Zr atom has an eight-coordinate dodecahedral environment being bonded to two bridging OH groups and three chelating oxalate ligands, but has no imposed crysallographic symmetry. The Zr…Zr non-bonded distance is 3.50(1) Å. The OZrO bridge angles are 69.7(4)° and A and 67.4(3)° in B.

Supporting schools in identifying and safeguarding the needs of disabled children: the challenges for data collection

Conceptualisations of disability that emphasise the contextual and cultural nature of disability and the embodiment of these within a national system of data collection present a number of challenges especially where this process is devolved to schools. The requirement for measures based on contextual and subjective experiences gives rise to particular difficulties in achieving parity in the way data is analysed and reported. This paper presents an account of the testing of a tool intended for use by schools as they collect data from parents to identify children who meet the criteria of disability established in Disability Discrimination Acts (DDAs). Data were validated through interviews with parents and teachers and observations of children and highlighted the pivotal role of the criterion of impact. The findings are set in the context of schools meeting their legal duties to identify disabled children and their support needs in a way that captures the complexity of disabled children’s school lives and provides useful and useable data.

Intercomparison and validation of the mixed layer depth fields of global ocean syntheses

Intercomparison and evaluation of the global ocean surface mixed layer depth (MLD) fields estimated from a suite of major ocean syntheses are conducted. Compared with the reference MLDs calculated from individual profiles, MLDs calculated from monthly mean and gridded profiles show negative biases of 10–20 m in early spring related to the re-stratification process of relatively deep mixed layers. Vertical resolution of profiles also influences the MLD estimation. MLDs are underestimated by approximately 5–7 (14–16) m with the vertical resolution of 25 (50) m when the criterion of potential density exceeding the 10-m value by 0.03 kg m−3 is used for the MLD estimation. Using the larger criterion (0.125 kg m−3) generally reduces the underestimations. In addition, positive biases greater than 100 m are found in wintertime subpolar regions when MLD criteria based on temperature are used. Biases of the reanalyses are due to both model errors and errors related to differences between the assimilation methods. The result shows that these errors are partially cancelled out through the ensemble averaging. Moreover, the bias in the ensemble mean field of the reanalyses is smaller than in the observation-only analyses. This is largely attributed to comparably higher resolutions of the reanalyses. The robust reproduction of both the seasonal cycle and interannual variability by the ensemble mean of the reanalyses indicates a great potential of the ensemble mean MLD field for investigating and monitoring upper ocean processes.

Representation type of Jordan algebras

The problem of classification of Jordan bit-nodules over (non-semisimple) finite dimensional Jordan algebras with respect to their representation type is considered. The notions of diagram of a Jordan algebra and of Jordan tensor algebra of a bimodule are introduced and a mapping Qui is constructed which associates to the diagram of a Jordan algebra J the quiver of its universal associative enveloping algebra S(J). The main results are concerned with Jordan algebras of semi-matrix type, that is, algebras whose semi-simple component is a direct sum of Jordan matrix algebras. In this case, criterion of finiteness and tameness for one-sided representations are obtained, in terms of diagram and mapping Qui, for Jordan tensor algebras and for algebras with radical square equals to 0. (c) 2010 Elsevier Inc. All rights reserved.

Duas vertentes da ontogênese da linguagem no desenvolvimento cognitivo

Este estudo pretende trazer uma contribuição à discussão da relação linguagem-cognição, através do exame de um aspecto restrito do problema: a hipótese de uma base cognitiva para aquisição de linguagem. O modelo teórico piagetiano é analisado em sua explicação da ontogenese da linguagem como resultante das construções da inteligência sensório-motora. Alguns de seus aspectos são questionados, a possibilidade de sua explicitação em forma de hipótese verificável é examinada e a literatura é analisada em busca de evidências relevantes. A principal lacuna constatada é a visão de linguagem restrita a aspectos de desempenho, sendo levado em conta apenas o começo da emissão de palavras na quase totalidade das pesquisas. Ainda dentro de uma perspectiva construtivista, o esboço de um novo modelo teórico é proposto, incluindo a discussão da ontogenese da compreensão de linguagem. Hipóteses decorrentes da proposta teórica, especialmente a de início da possibilidade de tratar o signo linguístico antes do estágio VI, são formuladas e verificadas por pesquisa empírica. Esta inclui um estudo longitudinal e outro transversal do desenvolvimento linguístico e cognitivo de 45 crianças entre 8 e 18 meses. O desenvolvimento da compreensão é comparado em diversos aspectos ao da produção ou fala. Verifica-se que o primeiro começa mais cedo, é mais rápido e atinge um vocabulário maior e um nível mais complexo na faixa etária estudada. Há evidências ainda de diferenças no papel da imitação na construção do vocabulário nas duas vertentes. Observa-se um início de resposta mais generalizada e sistemática à linguagem a partir de nove meses, ocasião em que a criança se mostra capaz de coordenação de reações circulares secundárias e quando consegue reconstruir mentalmente um objeto invisível a partir de uma fração visível. Considera-se que esta resposta já envolve a decodificação de signos e a diferenciação significante-significado, numa etapa preliminar de um processo evolutivo que se entrelaça com a formação de conceitos. Os dados nao permitem a identificação de prê-requisitos cognitivos para aquisição de liguagem, mas dois aspectos podem ser destacados como correlatos do início do processo de compartilhar o signo linguístico: a possibilidade da criança compreender que tem um nome e responder a ele e uma intencionalidade primitiva. Os resultados apoiam as hipóteses formuladas e sugerem que as construções finais do período sensório-motor não são condições necessárias para aquisição de linguagem e que esta não ê consequência direta do desenvolvimento cognitivo. Novos estudos são necessários para suprir as limitações desta pesquisa e verificação das implicações decorrentes dos resultados obtidos.

Comparison of the quantification of caffeine in human plasma by gas chromatography and ELISA

In the present study we evaluated the precision of the ELISA method to quantify caffeine in human plasma and compared the results with those obtained by gas chromatography. A total of 58 samples were analyzed by gas chromatography using a nitrogen-phosphorus detector and routine techniques. For the ELISA test, the samples were diluted to obtain a concentration corresponding to 50% of the absorbance of the standard curve. To determine whether the proximity between the I50 of the standard curve and that of the sample would bring about a more precise result, the samples were divided into three blocks according to the criterion of difference, in modulus, of the I50 of the standard curve and of the I50 of the sample. The samples were classified into three groups. The first was composed of 20 samples with I50 up to 1.5 ng/ml, the second consisted of 21 samples with I50 ranging from 1.51 to 3 ng/ml, and the third of 17 samples with I50 ranging from 3.01 to 13 ng/ml. The determination coefficient (R² = 0.999) showed that the data obtained by gas chromatography represented a reliable basis. The results obtained by ELISA were also reliable, with an estimated Pearson correlation coefficient of 0.82 between the two methods. This coefficient for the different groups (0.88, 0.79 and 0.49 for groups 1, 2 and 3, respectively) showed greater reliability for the test with dilutions closer to I50.

Trends of the genetic connectedness measures among Nelore beef cattle herds

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Otimização Topológica com Termo-elasticidade Utilizando Elementos Tri3

This work proposes a formulation for optimization of 2D-structure layouts submitted to mechanic and thermal shipments and applied an h-adaptive filter process which conduced to computational low spend and high definition structural layouts. The main goal of the formulation is to minimize the structure mass submitted to an effective state of stress of von Mises, with stability and lateral restriction variants. A criterion of global measurement was used for intents a parametric condition of stress fields. To avoid singularity problems was considerate a release on the stress restriction. On the optimization was used a material approach where the homogenized constructive equation was function of the material relative density. The intermediary density effective properties were represented for a SIMP-type artificial model. The problem was simplified by use of the method of finite elements of Galerkin using triangles with linear Lagrangian basis. On the solution of the optimization problem, was applied the augmented Lagrangian Method, that consists on minimum problem sequence solution with box-type restrictions, resolved by a 2nd orderprojection method which uses the method of the quasi-Newton without memory, during the problem process solution. This process reduces computational expends showing be more effective and solid. The results materialize more refined layouts with accurate topologic and shape of structure definitions. On the other hand formulation of mass minimization with global stress criterion provides to modeling ready structural layouts, with violation of the criterion of homogeneous distributed stress

Otimização de forma aplicando B-splines sob critério integral de tensões

This work proposes a computational methodology to solve problems of optimization in structural design. The application develops, implements and integrates methods for structural analysis, geometric modeling, design sensitivity analysis and optimization. So, the optimum design problem is particularized for plane stress case, with the objective to minimize the structural mass subject to a stress criterion. Notice that, these constraints must be evaluated at a series of discrete points, whose distribution should be dense enough in order to minimize the chance of any significant constraint violation between specified points. Therefore, the local stress constraints are transformed into a global stress measure reducing the computational cost in deriving the optimal shape design. The problem is approximated by Finite Element Method using Lagrangian triangular elements with six nodes, and use a automatic mesh generation with a mesh quality criterion of geometric element. The geometric modeling, i.e., the contour is defined by parametric curves of type B-splines, these curves hold suitable characteristics to implement the Shape Optimization Method, that uses the key points like design variables to determine the solution of minimum problem. A reliable tool for design sensitivity analysis is a prerequisite for performing interactive structural design, synthesis and optimization. General expressions for design sensitivity analysis are derived with respect to key points of B-splines. The method of design sensitivity analysis used is the adjoin approach and the analytical method. The formulation of the optimization problem applies the Augmented Lagrangian Method, which convert an optimization problem constrained problem in an unconstrained. The solution of the Augmented Lagrangian function is achieved by determining the analysis of sensitivity. Therefore, the optimization problem reduces to the solution of a sequence of problems with lateral limits constraints, which is solved by the Memoryless Quasi-Newton Method It is demonstrated by several examples that this new approach of analytical design sensitivity analysis of integrated shape design optimization with a global stress criterion purpose is computationally efficient

Isozyme characterization of Eucalyptus urophylla (S.T. Blake) and E-grandis (Hill ex Maiden) populations in Brazil

Seedling taken from 2 species of Eucalyptus growing in Brazil were electrophoretically analysed at 14 isozyme loci representing 6 enzyme systems: alpha-EST, beta-EST, SKDH, IDH, MDH, and LAP. Genetic variability measures were determined using 11 putative isozyme loci. on average, 81.8% and 54.5% of the loci were found to be polymorphic by the criterion of 95% in E. urophylla and E. grandis, respectively. The mean number of alleles per loci was 3.0 in E. urophylla and 2.5 in E. grandis. Observed mean heterozygosity was 0.283 in E. urophylla and 0.166 in E. grandis. Levels of genetic diversity in these species were similar to those in other Eucalyptus species which have widespread distributions. The possible hybridization of E. urophylla with E. alba is also discussed.

Taxonomic status of the genus Sotalia: Species level ranking for tucuxi (Sotalia fluviatilis) and costero (Sotalia guianensis) dolphins

Dolphins of the genus Sotalia are found along the Caribbean and Atlantic coasts of Central and South America and in the Amazon River and most of its tributaries. At present, the taxonomy of these dolphins remains unresolved. Although five species were described in the late 1800s, only one species is recognized currently (Sotalia fluviatilis) with two ecotypes or subspecies, the coastal subspecies (Sotalia fluviatilis guianensis) and the riverine subspecies (Sotalia fluviatilis fluviatilis). Recent morphometric analyses, as well as mitochondrial DNA analysis, suggested recognition of each subspecies as separate species. Here we review the history of the classification of this genus and present new genetic evidence from ten nuclear and three mitochondrial genes supporting the elevation of each subspecies to the species level under the Genealogical/Lineage Concordance Species Concept and the criterion of irreversible divergence. We also review additional evidence for this taxonomic revision from previously published and unpublished genetic, morphological, and ecological studies. We propose the common name costero for the coastal species, Sotalia guianensis (Van Beneden 1864), and accept the previously proposed tucuxi dolphin, Sotalia fluviatilis (Gervais, 1853), for the riverine species.

Automation and cybernetics: Control of a flexible one-link manipulator

States that control is of the essence in cybernetics. Summarizes the dynamic equations for a flexible one-link manipulator moving in the horizontal plane. Employs the finite element method, based on elementary beam theory, during the process of formulation. Develops and instruments a one-link flexible manipulator in order to control its vibration modes. Uses a simple second-order vibration model which permits vibrations on the rod to be estimated using the hub angle. The validation of the dynamic model and the structural analysis of the flexible manipulator is reached using proper infrared cameras and active light sources for determining actual positions of objects in space. Shows that the performance of the control is satisfactory, even under perturbation action.