23 resultados para bonding configuration

em Université de Lausanne, Switzerland


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The new complex, [Zr(pda)2]n (1, pda2- = N,N'-bis(neo-pentyl)-ortho-phenylenediamide, n = 1 or 2), prepared by the reaction of 2 equiv of pdaLi2 with ZrCl4, reacts rapidly with halogen oxidants to afford the new product ZrX2(disq)2 (3, X = Cl, Br, I; disq- = N,N'-bis(neo-pentyl)-ortho-diiminosemiquinonate) in which each redox-active ligand has been oxidized by one electron. The oxidation products 3a-c have been structurally characterized and display an unusual parallel stacked arrangement of the disq- ligands in the solid state, with a separation of approximately 3 A. Density functional calculations show a bonding-type interaction between the SOMOs of the disq- ligands to form a unique HOMO while the antibonding linear combination forms a unique LUMO. This orbital configuration leads to a closed-shell-singlet ground-state electron configuration (S = 0). Temperature-dependent magnetism measurements indicate a low-lying triplet excited state at approximately 750 cm-1. In solution, 3a-c show strong disq--based absorption bands that are invariant across the halide series. Taken together these spectroscopic measurements provide experimental values for the one- and two-electron energies that characterize the pi-stacked bonding interaction between the two disq- ligands.

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AIMS: This article explores the structures of relational resources that individuals with psychiatric disorders get from their family configurations using the concept of social capital. METHODS: The research is based on a sample of 54 individuals with psychiatric disorders and behavioural problems, and a comparison sample of 54 individuals without a clinical record matched to the clinical respondents for age and sex. Standard measures of social capital from social network methods are applied on family configurations of individuals from both samples. Differences are tested by variance analysis. RESULTS: Structures of family resources available to individuals with psychiatric disorders are distinct. Individuals with psychiatric disorders perceive themselves as less central in their family configurations and less connected to their family members. Their significant family members are perceived as less connected with each other. As a whole, their family configurations are smaller and do not include spouses or partners. Therefore bridging and bonding social capitals are not readily available for them. CONCLUSION: As family configurations of individuals with psychiatric disorders provide fewer relational resources than other families, they are not able to deal with social integration of individuals with psychiatric disorders on their own.

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Divorce and remarriage usually imply a redefinition of family boundaries, with consequences for the production and availability of social capital. This research shows that bonding and bridging social capitals are differentially made available by families. It first hypothesizes that bridging social capital is more likely to be developed in stepfamilies, and bonding social capital in first-time families. Second, the boundaries of family configurations are expected to vary within stepfamilies and within first-time families creating a diversity of family configurations within both structures. Third, in both cases, social capital is expected to depend on the ways in which their family boundaries are set up by individuals by including or excluding ex-partners, new partner's children, siblings, and other family ties. The study is based on a sample of 300 female respondents who have at least one child of their own between 5 and 13 years, 150 from a stepfamily structure and 150 from a first-time family structure. Social capital is empirically operationalized as perceived emotional support in family networks. The results show that individuals in first-time families more often develop bonding social capital and individuals in stepfamilies bridging social capital. In both cases, however, individuals in family configurations based on close blood and conjugal ties more frequently develop bonding social capital, whereas individuals in family configurations based on in-law, stepfamily or friendship ties are more likely to develop bridging social capital.

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It is frequently stated that unilateral cricothyroid muscle (CT) paralysis can be diagnosed by physical examination, noting rotation of the glottis, and shortening and vertical displacement of the ipsilateral vocal fold. These signs, however, are inconsistently observed, and there is considerable controversy regarding the direction of glottic rotation. To determine the effects of CT contraction on three-dimensional glottic configuration, we performed computerized tomography on cadaver larynges before and after simulated CT contraction. Radiopaque makers were used to compute distances. Unilateral CT contraction equally increased the length of both membranous vocal folds, and rotated the posterior glottis less than 1 mm. CT contraction neither adducted the vocal processes, nor significantly their altered vertical level. These results suggest that unilateral CT paralysis cannot be diagnosed on the basis of any clinically apparent change in glottal configuration.

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Most linguistic and interactional studies on public and media debates focus on the way talk-in- interaction is locally managed by the moderator. For example, they analyze the extent to which the questions asked are both sequentially and categorically relevant. The present paper aims at enriching these studies by discussing the profitability of a multimodal and longitudinal approach to membership categorization practices. The approach is multimodal in the sense that it does not focus exclusively on verbal features. The approach is also longitudinal by considering the extent to which a debate is pre- configured. To this end, particular attention is paid to the posters promoting the encounters and to the way the participants are positioned in physical space.

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The loss of biodiversity has become a matter of urgent concern and a better understanding of local drivers is crucial for conservation. Although environmental heterogeneity is recognized as an important determinant of biodiversity, this has rarely been tested using field data at management scale. We propose and provide evidence for the simple hypothesis that local species diversity is related to spatial environmental heterogeneity. Species partition the environment into habitats. Biodiversity is therefore expected to be influenced by two aspects of spatial heterogeneity: 1) the variability of environmental conditions, which will affect the number of types of habitat, and 2) the spatial configuration of habitats, which will affect the rates of ecological processes, such as dispersal or competition. Earlier, simulation experiments predicted that both aspects of heterogeneity will influence plant species richness at a particular site. For the first time, these predictions were tested for plant communities using field data, which we collected in a wooded pasture in the Swiss Jura mountains using a four-level hierarchical sampling design. Richness generally increased with increasing environmental variability and "roughness" (i.e. decreasing spatial aggregation). Effects occurred at all scales, but the nature of the effect changed with scale, suggesting a change in the underlying mechanisms, which will need to be taken into account if scaling up to larger landscapes. Although we found significant effects of environmental heterogeneity, other factors such as history could also be important determinants. If a relationship between environmental heterogeneity and species richness can be shown to be general, recently available high-resolution environmental data can be used to complement the assessment of patterns of local richness and improve the prediction of the effects of land use change based on mean site conditions or land use history.

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Disturbances affect metapopulations directly through reductions in population size and indirectly through habitat modification. We consider how metapopulation persistence is affected by different disturbance regimes and the way in which disturbances spread, when metapopulations are compact or elongated, using a stochastic spatially explicit model which includes metapopulation and habitat dynamics. We discover that the risk of population extinction is larger for spatially aggregated disturbances than for spatially random disturbances. By changing the spatial configuration of the patches in the system--leading to different proportions of edge and interior patches--we demonstrate that the probability of metapopulation extinction is smaller when the metapopulation is more compact. Both of these results become more pronounced when colonization connectivity decreases. Our results have important management implication as edge patches, which are invariably considered to be less important, may play an important role as disturbance refugia.

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La notion de développement durable structure le débat contemporain sur les finalités et les instruments des politiques publiques. La montée en puissance des préoccupations environnementales et de qualité des cadres de vie déplace les enjeux traditionnels de l'aménagement. Cette refonte s'inscrit dans une prise de conscience de la transversalité des problèmes de développement territorial. Une attention accrue est aussi portée aux acteurs et à leur participation invitant à repenser les articulations entre les élus, l'administration et la société civile. L'aménagement du territoire est à un tournant. La complexité accrue du champ décisionnel liée à la multiplicité des objectifs à prendre en compte, à la diversification des acteurs concernés, mais aussi à l'interférence des échelles de gouvernance bouscule les pratiques professionnelles. Cette note vise à montrer les principaux changements observés au cours des dernières années. Elle met l'accent sur la redéfinition des objectifs et des instruments d'aménagement et l'émergence des nouvelles pratiques de conduite de projets.