In this study, we focus on qualitative differences in the network structure and dynamics of natural as well as poly(butadiene) rubber in dependence of the cure system (sulfur/accelerator or organic peroxide) used in the vulcanization process. The spatial homogeneity of the distribution of chemical and physical cross-links in the network is assessed via the quantitative measurement of proton-proton residual dipolar couplings as measured by static multiple-quantum (MQ) NMR spectroscopy at low field. The experiment also provides information on the apparent correlation time of fast segmental fluctuations that dominate chain relaxation processes at lower temperature, for which we also find characteristic differences. Vulcanization via a radical mechanism (using organic peroxides) leads to networks with a high content of nonelastic defects (loops or dangling chains), a rather inhomogeneous distribution of cross-links, and modified (slower) local dynamics, as compared to networks obtained by sulfur vulcanization. These microstructural factors can be related with the well-known differences in the macroscopic properties of diene rubbers vulcanized with different cure systems.

Phylogenetic diversity measures rank areas for biodiversity conservation priorities based on information encoded in phylogenies (cladograms). The goal of these ranks for conservation is to consider as many factors as possible that provide additional taxic information, such as taxa richness, taxa distributional patterns, area endemicity, and complementarity between areas. At present there are many measures that consider phylogenetic information, including node-based, genetic-distance, and feature-based measures. We devised a modified phylogenetic node-based index that we call "taxonomic endemicity standardized weight," which considers not only the taxonomic distinctness of the taxa that inhabit a given area but their endemicity as well. Once the standardized weight of the taxonomic endemicity identifies the area of highest priority, complementarity can be used to identify the second area and so on. We used this node-based index to rank priority areas for conservation in southern South America, and we compared the results of our rankings to results based on other node-based indexes. Our index identified Santiago district, in Central Chile province, as the highest priority area for conservation, followed by Maule, Malvinas, and districts of Subantarctic province. Malvinas exhibits greater complementarity relative to Santiago than Maule does, however, so Malvinas is ranked second in priority. Indexes based on phylogenetic information measure the evolutionary component of biodiversity and allow one to identify areas that will ensure the preservation of evolutionary potential and phylogenetically rare taxa. The modified index we propose is sensitive to taxic distinctness and endemicity as well and allows information from diverse taxa to be combined (i.e., different cladograms). The use of complementarity allows for preservation of the maximum quantity of taxa in a minimal number of protected areas. Utilización de Medidas de Diversidad Filogenética para Definir Prioridades en Conservación: un Ejemplo del Sur de América del SurResumen: Las medidas de diversidad filogenética jerarquiza a las áreas para prioridades de conservación de biodiversidad con base en información codificada en filogenias (cladogramas), La meta de estas categorías de conservación requiere tomar en consideración tantos factores que proporcionan información adicional (riqueza de taxones, patrones de distribución de los taxones, endemicidad del área y complementariedad entre áreas) como sea posible. Actualmente hay muchas medidas que consideran información filogenética (basadas en nodos, distancia genética y basadas en características). Diseñamos un índice filogenético modificado basado en nodos que denominamos "peso estandarizado de endemicidad taxonómica", el cual considera no solo la peculiaridad genética de los taxa que habitan una región determinada sino también su endemicidad. Una vez que el peso estandarizado de endemicidad identifica el área de mayor prioridad, la complementariedad se puede usar para identificar la segunda área y así sucesivame...

The network structure and chain dynamics of ionic elastomers based on carboxylated nitrile rubber (XNBR) cross-linked with different content of magnesium oxide (MgO) have been studied by different low-field time-domain NMR experiments. Ionic contacts created during the vulcanization tend to aggregate trapping some polymer segments that show restricted mobility as it was quantified by analyses of refocused free induction decays. Increasing the MgO content above the stoichiometric fraction has no effect on the amount of trapped polymer segments, but it increases the network cross-link density as measured by multiple-quantum (MQ) NMR experiments. The central finding of this work is that MgO addition above the stoichiometric content enhances the mechanical properties by creating a larger number of smaller ionic clusters, which act as dynamic cross-links, but are not readily seen by other techniques. Changes in the network structure and morphology of segregated thermolabile ionic domains have an impact on the ionic rearrangement dynamics and, in consequence, on the thermoplastic behavior of these materials at elevated temperatures.

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