859 resultados para BORON-CENTERED RADICALS


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Modern writers like Djuna Barnes allow for the post-modern fluidity and explosion of sex and gender without finalizing either in a fixed form. Whereas the classical, archetypal androgyne is made up of two halves, one man and one woman; the deconstructed androgynous figure is not constituted of oppositional terms which would reflect an essential and unimpeachable truth. I reveal the way Djuna Barnes’ Nightwood not only thematizes the fluid androgyne, but also cleverly verbalizes David Wood’s perpetual and un-dischargable “debt” to extra-discursivity while poetically critiquing gender “appropriateness,” societal constraints, and the constitution of identity. Barnes presents a decentralized, ungrounded and non-prescribed world in Nightwood not only through her cross-dressing and androgynous characters, but also in her poetics, her assertion of the open-ended quality of language, and a strong imperative to negotiate our physical existence in a world of fluid gender and sexual boundaries.

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The purpose of this thesis was to examine the mediating effects of job-related negative emotions on the relationship between workplace aggression and outcomes. Additionally, the moderating effects of workplace social support and intensity of workplace aggression are considered. A total 321 of working individuals participated through an online survey. The results of this thesis suggest that job-related negative emotions are a mediator of the relationship between workplace aggression and outcomes, with full and partial mediation supported. Workplace social support was found to be a buffering variable in the relationship between workplace aggression and outcomes, regardless of the source of aggression (supervisor or co-worker) or the source of the social support. Finally, intensity of aggression was found to be a strong moderator of the relationship between workplace aggression and outcomes.

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Improved clinical care for Bipolar Disorder (BD) relies on the identification of diagnostic markers that can reliably detect disease-related signals in clinically heterogeneous populations. At the very least, diagnostic markers should be able to differentiate patients with BD from healthy individuals and from individuals at familial risk for BD who either remain well or develop other psychopathology, most commonly Major Depressive Disorder (MDD). These issues are particularly pertinent to the development of translational applications of neuroimaging as they represent challenges for which clinical observation alone is insufficient. We therefore applied pattern classification to task-based functional magnetic resonance imaging (fMRI) data of the n-back working memory task, to test their predictive value in differentiating patients with BD (n=30) from healthy individuals (n=30) and from patients' relatives who were either diagnosed with MDD (n=30) or were free of any personal lifetime history of psychopathology (n=30). Diagnostic stability in these groups was confirmed with 4-year prospective follow-up. Task-based activation patterns from the fMRI data were analyzed with Gaussian Process Classifiers (GPC), a machine learning approach to detecting multivariate patterns in neuroimaging datasets. Consistent significant classification results were only obtained using data from the 3-back versus 0-back contrast. Using contrast, patients with BD were correctly classified compared to unrelated healthy individuals with an accuracy of 83.5%, sensitivity of 84.6% and specificity of 92.3%. Classification accuracy, sensitivity and specificity when comparing patients with BD to their relatives with MDD, were respectively 73.1%, 53.9% and 94.5%. Classification accuracy, sensitivity and specificity when comparing patients with BD to their healthy relatives were respectively 81.8%, 72.7% and 90.9%. We show that significant individual classification can be achieved using whole brain pattern analysis of task-based working memory fMRI data. The high accuracy and specificity achieved by all three classifiers suggest that multivariate pattern recognition analyses can aid clinicians in the clinical care of BD in situations of true clinical uncertainty regarding the diagnosis and prognosis.

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Background: This study aimed to describe the developmental trajectories of registered nurses' capability beliefs during their first 3 years of practice. The focus was on three core competencies for health professionals-patient-centered care, teamwork, and evidence-based practice. Methods: A national cohort of registered nurses (n = 1,205) was recruited during their nursing education and subsequently surveyed yearly during the first 3 years of working life. The survey included 16 items on capability beliefs divided into three subscales for the assessment of patient-centered care, teamwork, and evidence-based practice, and the data were analyzed with linear latent growth modeling. Results: The nurses' capability beliefs for patient-centered care increased over the three first years of working life, their capability beliefs for evidence-based practice were stable over the 3 years, and their capability beliefs for teamwork showed a downward trend. Linking evidence to action: Through collaboration between nursing education and clinical practice, the transition to work life could be supported and competence development in newly graduated nurses could be enhanced to help them master the core competencies. Future research should focus on determining which factors impact the development of capability beliefs in new nurses and how these factors can be developed by testing interventions.

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Phytoremediation studies have been conducted in an area contaminated by heavy metals, located in Piracicaba - SP, Brazil. This area was contaminated accidentally by the addition of auto scrap shredding to the soil and was limed later to reduce heavy metal mobility in the environment. Previous characterization showed that it also presents high concentration of boron, which has limited the initial plant development of some species. As sunflower plants require a high boron supply and the literature describes its use in the phytoremediation of soils contaminated with heavy metals under some conditions, the aim of this work was to evaluate its potential for the remediation of this area. In the present study, the results of preliminary tests are presented, aiming at the evaluation of sunflower plant germination and its initial development when cultivated in the contaminated soil described. Two sunflower hybrids were sown in soils treated with different rates of boron and in the soil from the contaminated area in study. The results showed that sunflower plants had a normal initial development, even in the soil from the contaminated area. Therefore, sunflower is a promising crop and further studies will be developed to evaluate the sunflower efficiency in phytoextraction or phytostabilization of heavy metals in areas where boron contamination also occurs, as is the case in the study area.

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The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).

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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

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Even though today’s corporations recognize that they need to understand modern project management techniques (Schwalbe, 2002, p2), many researchers continue to provide evidence of poor IT project success. With Kotnour, (2000) finding that project performance is positively associated with project knowledge, a better understanding of how to effectively manage knowledge in IT projects should have considerable practical significance for increasing the chances of project success. Using a combined qualitative/quantitative method of data collection in multiple case studies spanning four continents, and comprising a variety of organizational types, the focus of this current research centered on the question of why individuals working within IT project teams might be motivated towards, or inhibited from, sharing their knowledge and experience in their activities, procedures, and processes. The research concluded with the development of a new theoretical model of knowledge sharing behavior, ‘The Alignment Model of Motivational Focus’. This model suggests that an individual’s propensity to share knowledge and experience is a function of perceived personal benefits and costs associated with the activity, balanced against the individual’s alignment to a group of ‘institutional’ factors. These factors are identified as alignments to the project team, to the organization, and dependent on the circumstances, to either the professional discipline or community of practice, to which the individual belongs.

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The process-centered design of organizations and information systems is globally seen as an appropriate response to the increased economic pressure on organizations. At the methodological core of process-centered management is process modeling. However, business process modeling in large initiatives can be a time-consuming and costly exercise, making it potentially difficult to convince executive management of its benefits. To date, and despite substantial interest and research in the area of process modeling, the understanding of the actual benefits of process modeling in academia and practice is limited. To address this gap, this paper explores the perception of benefits derived from process modeling initiatives, as reported through a global Delphi study. The study incorporates the views of three groups of stakeholders – academics, practitioners and vendors. Our findings lead to the first identification and ranking of 19 unique benefits associated with process modeling. The study in particular found that process modeling benefits vary significantly between practitioners and academics. We argue that these variations may point to a dangerous disconnect between research projects and practical demands.

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Principal topic: Effectuation theory suggests that entrepreneurs develop their new ventures in an iterative way by selecting possibilities through flexibility and interactions with the market; a focus on affordability of loss rather than maximal return on the capital invested, and the development of pre-commitments and alliances from stakeholders (Sarasvathy, 2001, 2008; Sarasvathy et al., 2005, 2006). In contrast, causation may be described as a rationalistic reasoning method to create a company. After a comprehensive market analysis to discover opportunities, the entrepreneur will select the alternative with the higher expected return and implement it through the use of a business plan. However, little is known about the consequences of following either of these two processes. One aspect that remains unclear is the relationship between newness and effectuation. On one hand it can be argued that the combination of a means-centered, interactive (through pre-commitments and alliances with stakeholders from the early phases of the venture creation) and open-minded process (through flexibility of exploiting contingencies) should encourage and facilitate the development of innovative solutions. On the other hand, having a close relationship with their “future first customers” and focussing too much on the resources and knowledge already within the firm may be a constraint that is not conducive to innovation, or at least not to a radical innovation. While it has been suggested that effectuation strategy is more likely to be used by innovative entrepreneurs (Sarasvathy, 2001), this hypothesis has not been demonstrated yet (Sarasvathy, 2001). Method: In our attempt to capture newness in its different aspects we have considered the following four domains where newness may happen: new product/service; new method for promotion and sales; new production methods/sourcing; market creation. We identified how effectuation may be differently associated with these four domains of newness. To test our four sets of hypotheses a dataset of 1329 firms (702 nascent and 627 young firms) randomly selected in Australia was examined through ANOVA Tukey HSD Test. Results and Implications: Results indicate the existence of a curvilinear relationship between effectuation and newness where low and high levels of newness are associated with low level of effectuation while medium level of newness is associated with high level of effectuation. Implications for academia, practitioners and policy makers are also discussed.

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Theories on teaching and learning for adult learners are constantly being reviewed and discussed in the higher educational environment. Theories are not static and appear to be in a constant developmental process. This paper discusses three of these theories: pedagogy, andragogy and heutagogy. It is argued that although educators engage in many of the principles of either student-centered (andragogy) and self-determined (heutagogy) learning, it is not possible to fully implement either theory. The two main limitations are the requirements of both internal and external stakeholders, such as accrediting bodies and requirements to assess all student learning. A reversion to teacher-centered learning (pedagogy) ensues. In summary, we engage in many action-oriented learning activities but revert to teacher-centered approaches in terms of content and assessment.

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In this paper we respond to calls for an institution-based perspective on strategy. With its emphasis upon mimetic, coercive, and normative isomorphism, institutional theory has earned a deterministic reputation and seems an unlikely foundation on which to construct a theory of strategy. However, a second movement in institutional theory is emerging that gives greater emphasis to creativity and agency. We develop this approach by highlighting co-evolutionary processes that are shaping the varieties of capitalism (VoC) in Asia. To do so, we examine the extent to which the VoC model can be fruitfully applied in the Asian context. In the spirit of the second movement of institutional theory, we describe three processes in which firm strategy collectively and intentionally feeds back to shape institutions: (1) filling institutional voids, (2) retarding institutional innovation, and (3) deploying institutional escape. We outline the key contributions contained in the articles of this Special Issue and discuss a research agenda generated by the VoC perspective.

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SITDRM 1 is a privacy protection system that protects private data through the enforcement of MPEG REL licenses provided by consumers. Direct issuing of licenses by consumers has several usability problems that will be mentioned in this paper. Further, we will describe how SITDRM incorporates P3P language to provide a consumer-centered privacy protection system.