Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

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

Le poids de la notion Tesniérienne de centralité du verbe dans les analyses linguistiques

This paper examines the historical role that Tesnière’s theory on the centrality of the verb exerted on some theoretical branches that study the way utterances are built in language. The main goal of this paper is to evaluate the impact that such a proposal had in changing the view of the clause being purely logical (a proposition) or purely syntactic (abstractly equated) to a view that embodies semantics and pragmatics to the syntactic organization of the utterance. A close examination of research dedicated to the grammatical and lexicographic description of Portuguese helps to illustrate the here proposed assessment and contributes to support the claim of the influence of Tesnière on current linguistic analyses.

A joint experimental and theoretical study on the electronic structure and photoluminescence properties of Al-2(WO4)(3) powders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Theoretical models for the antitrypanosomal activity of thiosemicarbazone derivatives

Thiosemicarbazones are cruzain inhibitors which have been identified as potential antitrypanosomal agents. In this work, several molecular properties were calculated at the density functional theory (DFT)/B3LYP/6-311G* level for a set of 44 thiosemicarbazones. Unsupervised and supervised pattern recognition techniques (hierarchical cluster analysis, principal component analysis, kth-nearest neighbors, and soft independent modeling by class analogy) were used to obtain structureactivity relationship models, which are able to classify unknown compounds according to their activities. The chemometric analyses performed here revealed that 12 descriptors can be considered responsible for the discrimination between high and low activity compounds. Classification models were validated with an external test set, showing that predictive classifications were achieved with the selected variable set. The results obtained here are in good agreement with previous findings from the literature, suggesting that our models can be useful on further investigations on the molecular determinants for the antichagasic activity. (C) 2012 Wiley Periodicals, Inc.

A graph-theoretical approach in brain functional networks. Possible implications in EEG studies

Abstract Background Recently, it was realized that the functional connectivity networks estimated from actual brain-imaging technologies (MEG, fMRI and EEG) can be analyzed by means of the graph theory, that is a mathematical representation of a network, which is essentially reduced to nodes and connections between them. Methods We used high-resolution EEG technology to enhance the poor spatial information of the EEG activity on the scalp and it gives a measure of the electrical activity on the cortical surface. Afterwards, we used the Directed Transfer Function (DTF) that is a multivariate spectral measure for the estimation of the directional influences between any given pair of channels in a multivariate dataset. Finally, a graph theoretical approach was used to model the brain networks as graphs. These methods were used to analyze the structure of cortical connectivity during the attempt to move a paralyzed limb in a group (N=5) of spinal cord injured patients and during the movement execution in a group (N=5) of healthy subjects. Results Analysis performed on the cortical networks estimated from the group of normal and SCI patients revealed that both groups present few nodes with a high out-degree value (i.e. outgoing links). This property is valid in the networks estimated for all the frequency bands investigated. In particular, cingulate motor areas (CMAs) ROIs act as ‘‘hubs’’ for the outflow of information in both groups, SCI and healthy. Results also suggest that spinal cord injuries affect the functional architecture of the cortical network sub-serving the volition of motor acts mainly in its local feature property. In particular, a higher local efficiency El can be observed in the SCI patients for three frequency bands, theta (3-6 Hz), alpha (7-12 Hz) and beta (13-29 Hz). By taking into account all the possible pathways between different ROI couples, we were able to separate clearly the network properties of the SCI group from the CTRL group. In particular, we report a sort of compensatory mechanism in the SCI patients for the Theta (3-6 Hz) frequency band, indicating a higher level of “activation” Ω within the cortical network during the motor task. The activation index is directly related to diffusion, a type of dynamics that underlies several biological systems including possible spreading of neuronal activation across several cortical regions. Conclusions The present study aims at demonstrating the possible applications of graph theoretical approaches in the analyses of brain functional connectivity from EEG signals. In particular, the methodological aspects of the i) cortical activity from scalp EEG signals, ii) functional connectivity estimations iii) graph theoretical indexes are emphasized in the present paper to show their impact in a real application.

Theoretical models to predict the mechanical behavior of thick composite tubes

This paper shows theoretical models (analytical formulations) to predict the mechanical behavior of thick composite tubes and how some parameters can influence this behavior. Thus, firstly, it was developed the analytical formulations for a pressurized tube made of composite material with a single thick ply and only one lamination angle. For this case, the stress distribution and the displacement fields are investigated as function of different lamination angles and reinforcement volume fractions. The results obtained by the theoretical model are physic consistent and coherent with the literature information. After that, the previous formulations are extended in order to predict the mechanical behavior of a thick laminated tube. Both analytical formulations are implemented as a computational tool via Matlab code. The results obtained by the computational tool are compared to the finite element analyses, and the stress distribution is considered coherent. Moreover, the engineering computational tool is used to perform failure analysis, using different types of failure criteria, which identifies the damaged ply and the mode of failure.

Facets of Gender : Analyses of the Family and the Labour Market

This thesis contains four different studies on the dynamics of gender in households and workplaces. The relationship between family life and work life is in focus, particularly in the paper on labour market outcomes after divorce. In the introductory chapter, the Swedish context is briefly described. The description focuses on gender differences in the labour market and in the home. Theories concerning the division of work in the household are discussed, as are two theories on labour market discrimination, viz. taste discrimination and statistical discrimination. The theory part is concluded with a discussion of social closure processes and gendered organizational structures. The Reproduction of Gender. Housework and Attitudes Towards Gender Equality in the Home Among Swedish Boys and Girls. The housework boys and girls age 10 to 18 do, and their attitudes towards gender equality in the home are studied. One aim is to see whether the work children do is gendered and if so, whether they follow their parents’, often gendered, pattern in housework. A second aim is to see whether parents’ division of work is related to the children’s attitude towards gender equality in the home. The data used are taken from the Swedish Child Level of Living Survey (Child-LNU) 2000. Results indicate that girls and boys in two-parent families are more prone to engage in gender-atypical work the more their parent of the same sex engages in this kind of work. The fact that girls still do more housework than boys indicates that housework is gendered work also among children. No relation between parents’ division of work and the child’s attitude towards gender equality in the home was found. Dependence within Families and the Household Division of Labor – A Comparison between Sweden and the United States. This paper assesses the relative explanatory value of the resource-bargaining perspective and the doing-gender approach in analysing the division of housework in the United States and Sweden from the mid-1970s to 2000. Data from the Swedish Level of Living Survey (LNU) and the Panel Study of Income Dynamics (PSID) were used. Overall results indicate that housework is truly gendered work in both countries during the entire period. Even so, the results also indicate that gender deviance neutralization is more pronounced in the United States than in Sweden. Unlike Swedish women, American women seem to increase their time spent in housework when their husbands are to some extent economically dependent on them, as if to neutralize the presumed gender deviance. Divorce and Labour Market Outcomes. Do Women Suffer or Gain? In this paper, the interconnected nature of work and family is studied by looking at labour market outcomes after divorce. The data used are retrospective work and family histories collected in LNU 1991. A hazard regression model with competing risks reveals that women’s chances of improving their occupational prestige appear to be better after divorce compared to before. Increased working hours and perhaps also increased energy invested in the job may pay off in better occupational opportunities. Worth noting, however, is that the outcome among women with a less firm labour market attachment is more often to a job of lower prestige than one of higher prestige. Hence, the labour market outcome for women after divorce is to some extent conditioned by their labour market attachment at the time of divorce. Men, on the other hand, in most cases seem to suffer occupationally from divorce. For separated men the risk of negative changes in occupational prestige is greater than for cohabiting men. Formal On-the-job Training. A Gender-Typed Experience and Wage- Related Advantage? Formal on-the-job training (FOJT) can have a positive impact on wages and on promotion opportunities. According to theory and earlier research, a two-step model of gender inequality in FOJT is predicted: First, women are less likely than men to take part in FOJT and, second, once women do get the more remunerative training, they are not rewarded for their new skills to the same extent as men are. Pooled cross-sectional data from the Swedish Survey of Living Conditions (ULF) in the mid-nineties were used. Results show that women are significantly less likely than men to take part in FOJT. Among those who do receive training, women are more likely to take part in industry-specific training, whereas men are more likely to participate in general training and training that increases promotion opportunities. The two latter forms of training significantly raise a man’s annual earnings but not a woman’s. Hence, the theoretical model is supported and it is argued that this gender inequality is partly due to employers’ discriminatory practices.

Development and application of a GC system for NMHC analyses of air samples from the CARIBIC aircraft project

The subject of this thesis is the development of a Gaschromatography (GC) system for non-methane hydrocarbons (NMHCs) and measurement of samples within the project CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com). Air samples collected at cruising altitude from the upper troposphere and lowermost stratosphere contain hydrocarbons at low levels (ppt range), which imposes substantial demands on detection limits. Full automation enabled to maintain constant conditions during the sample processing and analyses. Additionally, automation allows overnight operation thus saving time. A gas chromatography using flame ionization detection (FID) together with the dual column approach enables simultaneous detection with almost equal carbon atom response for all hydrocarbons except for ethyne. The first part of this thesis presents the technical descriptions of individual parts of the analytical system. Apart from the sample treatment and calibration procedures, the sample collector is described. The second part deals with analytical performance of the GC system by discussing tests that had been made. Finally, results for measurement flight are assessed in terms of quality of the data and two flights are discussed in detail. Analytical performance is characterized using detection limits for each compound, using uncertainties for each compound, using tests of calibration mixture conditioning and carbon dioxide trap to find out their influence on analyses, and finally by comparing the responses of calibrated substances during period when analyses of the flights were made. Comparison of both systems shows good agreement. However, because of insufficient capacity of the CO2 trap the signal of one column was suppressed due to breakthroughed carbon dioxide so much that its results appeared to be unreliable. Plausibility tests for the internal consistency of the given data sets are based on common patterns exhibited by tropospheric NMHCs. All tests show that samples from the first flights do not comply with the expected pattern. Additionally, detected alkene artefacts suggest potential problems with storing or contamination within all measurement flights. Two last flights # 130-133 and # 166-169 comply with the tests therefore their detailed analysis is made. Samples were analyzed in terms of their origin (troposphere vs. stratosphere, backward trajectories), their aging (NMHCs ratios) and detected plumes were compared to chemical signatures of Asian outflows. In the last chapter a future development of the presented system with focus on separation is drawn. An extensive appendix documents all important aspects of the dissertation from theoretical introduction through illustration of sample treatment to overview diagrams for the measured flights.

Anti-Americanism in Europe: Theoretical Mechanisms and Empirical Evidence

One of the most popular explanations for post-9/11 anti-Americanism argues that resentment against America and Americans is mainly a function of the US government’s unpopular actions. The present article challenges this interpretation: first, it argues that neither the vitality of the resentment in times when the United States had no influence in the respective parts of the world nor its recent radical manifestations are accounted for in a political reductionist framework. In fact, specific traditions of anti-Americanism have an influence on the negative attitudes observed today, as a comparison between Britain, France, Germany, and Poland reveals. Second, this article suggests an alternative theoretical approach. Anti-Americanism can be explained by two basic mechanisms: it functions as a strategy to project denied and disliked self-concepts onto an external object, and it offers an interpretation frame for complex social processes that allows to reduce cognitive dissonance. Multivariate analyses based on empirical data collected in the Pew surveys of 2002 and 2007 show the fruitfulness of our theoretical approach.

Transgressive sporting bodies - A theoretical and critical dicourse analysis of the representation of Caster Semenya in Swiss print media

A debate about Caster Semenya's female sex began shortly after the South African runner won gold in the women’s 800m final at the 2009 Athletic World Championships held in Berlin. Her victory was disputed through questions about her right to compete as a ‘woman’, with the International Association of Athletics Federation (IAAF) announcing she would be required to undergo a gender verification test before her victory could be confirmed. Using the theoretical frame of social constructionism (Berger & Luckmann), poststructuralism (Foucault), gender- and postcolonial theories (Butler; Hall; Spivak) and the methodology of critical discourse analysis (Jaeger), the paper explores the way the possible intersexuality of Caster Semenya was contextualised in mainstream Swiss German-language print media. The analyses will firstly look at the way in which Caster Semenya was constructed as a ʻfallen hero’ and stigmatised as a double-dealer and unacceptable deviant body. The rumours amongst athletes and commentators became news in the media, which focused on descriptions of her habitus, her muscular body and her deep voice. Through theoretical discussion the paper argues that the media response to Caster Semenya exemplifies Butler’s claim that the discursive framework of gender constructs and naturalises sex. A key question is therefore whether the designation of deviant bodies to a ʻfield of deformation’ (Butler) works to pluralise the field of gender, or rather, as Butler suggests, it tends that those bodies might call into questions. The final part of the paper discusses how gender, ethnicity and sexuality combine to constitute the black female sporting body as a spectacle of otherness. It is evident that this otherness is made manifest through the function of those bodies as a site of transgression, as the boundary between male and female, and often as the boundary between culture and nature (Hall). Using the example of the controversy surrounding Caster Semenya, this paper aims to demonstrate how the post/colonial white female body is reproduced by western norms of gender, sexuality, beauty and sporting behaviour, in the sense of a feminine sporting genderperformance. The media controversy will be also read through the lens of the globalisation of certain ideas of normative bodies, sex, ethnicity and gender and the challenge of changing stereotypes through transgression. Keywords: gender- and postcolonial theories, discourse analysis, print media, Caster Semen-ya, deviant body, ethnicity, intersexuality

Transgressive sporting bodies - A theoretical and critical dicourse analysis of the representation of Caster Semenya in Swiss print media

A debate about Caster Semenya's female sex began shortly after the South African runner won gold in the women’s 800m final at the 2009 Athletic World Championships held in Berlin. Her victory was disputed through questions about her right to compete as a ‘woman’, with the International Association of Athletics Federation (IAAF) announcing she would be required to undergo a gender verification test before her victory could be confirmed. Using the theoretical frame of social constructionism (Berger & Luckmann), poststructuralism (Foucault), gender- and postcolonial theories (Butler; Hall; Spivak) and the methodology of critical discourse analysis (Jaeger), the paper explores the way the possible intersexuality of Caster Semenya was contextualised in mainstream Swiss German-language print media. The analyses will firstly look at the way in which Caster Semenya was constructed as a ʻfallen hero’ and stigmatised as a double-dealer and unacceptable deviant body. The rumours amongst athletes and commentators became news in the media, which focused on descriptions of her habitus, her muscular body and her deep voice. Through theoretical discussion the paper argues that the media response to Caster Semenya exemplifies Butler’s claim that the discursive framework of gender constructs and naturalises sex. A key question is therefore whether the designation of deviant bodies to a ʻfield of deformation’ (Butler) works to pluralise the field of gender, or rather, as Butler suggests, it tends that those bodies might call into questions. The final part of the paper discusses how gender, ethnicity and sexuality combine to constitute the black female sporting body as a spectacle of otherness. It is evident that this otherness is made manifest through the function of those bodies as a site of transgression, as the boundary between male and female, and often as the boundary between culture and nature (Hall). Using the example of the controversy surrounding Caster Semenya, this paper aims to demonstrate how the post/colonial white female body is reproduced by western norms of gender, sexuality, beauty and sporting behaviour, in the sense of a feminine sporting genderperformance. The media controversy will be also read through the lens of the globalisation of certain ideas of normative bodies, sex, ethnicity and gender and the challenge of changing stereotypes through transgression. Keywords: gender- and postcolonial theories, discourse analysis, print media, Caster Semen-ya, deviant body, ethnicity, intersexuality

Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets

The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers.

Prototype emitter for use in subsurface drip irrigation: Manufacturing, hydraulic evaluation and experimental analyses

The current research aims to analyse theoretically and evaluate a self-manufactured simple design for subsurface drip irrigation (SDI) emitter to avoid root and soil intrusion. It was composed of three concentric cylindrical elements: an elastic silicone membrane; a polyethylene tube with two holes drilled on its wall for water discharge; and a vinyl polychloride protector system to wrap the other elements. The discharge of the emitter depends on the change in the membrane diameter when it is deformed by the water pressure. The study of the operation of this emitter is a new approach that considers mechanical and hydraulic principles. Thus, the estimation on the membrane deformation was based on classical mechanical stress theories in composite cylinders. The hydraulic principles considered the solid deformation due to force based on water pressure and the general Darcy–Weisbach head-loss equation. Twenty emitter units, with the selected design, were handcrafted in a lathe and were used in this study. The measured pressure/discharge relationship for the emitters showed good agreement with that calculated by the theoretical approach. The variation coefficient of the handcrafted emitters was high compared to commercial emitters. Results from field evaluations showed variable values for the relative flow variation, water emission uniformity and relative flow rate coefficients, but no emitter was obstructed. Therefore, the current emitter design could be suitable for SDI following further studies to develop a final prototype.

Subclinical social anxiety and academic performance in adolescence: analysis of theoretical and practical implications

This study analyses the relationship between self-reported social anxiety and academic performance in a sample of 1,616 Spanish students (52.1% males) in compulsory secondary education, aged 12 to 16 years old. Social anxiety was assessed by the Social Phobia and Anxiety Inventory (SPAI) and academic performance was measured with school grades and failing grades. Results reveal that adolescents with social anxiety show a similar academic performance to adolescents without social anxiety. Although t tests found some significant differences in academic grades and number of failing grades, the effect size analysis showed that these differences had no empirical relevance. These findings are discussed considering the gender and grade levels and their theoretical and practical implication.

The Economics of State Aid for the Rescue and Restructuring of Firms in Difficulty: Theoretical Considerations, Empirical Analysis and Proposals for Reform. Bruges European Economic Research (BEER) Papers 27/September 2013

State aid for rescue and restructuring (R&R) of companies in difficulty causes a significant distortion of competition. It prevents the market from eliminating inefficient companies. Because of this, the European Commission has to be specially strict when it assesses rescue or restructuring aid. This paper examines recent cases of corporate restructuring partly funded with public money. It explains the main aspects of the current guidelines which are applicable to R&R State Aid and establishes a theoretical framework for the economic assessment of R&R aid. It then analyses decisions adopted by the European Commission concerning R&R state aid during the period 2000-2013. It finds that there is little economic rationale in the granting of R&R aid. The paper concludes by applying the lessons drawn from the empirical analysis to the anticipated revision of the R&R guidelines in the context of the State Aid Modernisation process.