Suchergebnisse

The C-alkyl groups of cationic triruthenium cluster complexes of the type [Ru3(μ-H)(μ-κ2N1,C2 -L)(CO)10]+ (HL represents a generic C-alkyl-N- methylpyrazium species) have been deprotonated to give kinetic products that contain unprecedented C-alkylidene derivatives and maintain the original edge-bridged decacarbonyl structure. When the starting complexes contain various C-alkyl groups, the selectivity of these deprotonation reactions is related to the atomic charges of the alkyl H atoms, as suggested by DFT/natural-bond orbital (NBO) calculations. Three additional electronic properties of the C-alkyl C-H bonds have also been found to correlate with the experimental regioselectivity because, in all cases, the deprotonated C-H bond has the smallest electron density at the bond critical point, the greatest Laplacian of the electron density at the bond critical point, and the greatest total energy density ratio at the bond critical point (computed by using the quantum theory of atoms in molecules, QTAIM). The kinetic decacarbonyl products evolve, under appropriate reaction conditions that depend upon the position of the C-alkylidene group in the heterocyclic ring, toward face-capped nonacarbonyl derivatives (thermodynamic products). The position of the C-alkylidene group in the heterocyclic ring determines the distribution of single and double bonds within the ligand ring, which strongly affects the stability of the neutral decacarbonyl complexes and the way these ligands coordinate to the metal atoms in the nonacarbonyl products. The mechanisms of these decacarbonylation processes have been investigated by DFT methods, which have rationalized the structures observed for the final products and have shed light on the different kinetic and thermodynamic stabilities of the reaction intermediates, thus explaining the reaction conditions experimentally required by each transformation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. ; This work has been supported by the Spanish MICINN-FEDER grants CTQ2010–14933, MAT2010–15094, CSD2006–00015, and DELACIERVA-09–05; the European Union Marie Curie action FP7–2010-RG-268329; and a Severo Ochoa fellowship from Principado de Asturias (V.P.). ; Peer Reviewed

Abstract. Coastal areas are highly exposed to natural hazards associated with the sea. In all cases where there is historical evidence for devastating tsunamis, as is the case of the southern coasts of the Iberian Peninsula, there is a need for quantitative hazard tsunami assessment to support spatial planning. Also, local authorities must be able to act towards the population protection in a preemptive way, to inform "what to do" and "where to go" and in an alarm, to make people aware of the incoming danger. With this in mind, we investigated the inundation extent, run-up and water depths, of a 1755-like event on the region of Huelva, located on the Spanish southwestern coast, one of the regions that was affected in the past by several high energy events, as proved by historical documents and sedimentological data. Modelling was made with a slightly modified version of the COMCOT (Cornell Multi-grid Coupled Tsunami Model) code. Sensitivity tests were performed for a single source in order to understand the relevance and influence of the source parameters in the inundation extent and the fundamental impact parameters. We show that a 1755-like event will have a dramatic impact in a large area close to Huelva inundating an area between 82 and 92 km2 and reaching maximum run-up around 5 m. In this sense our results show that small variations on the characteristics of the tsunami source are not too significant for the impact assessment. We show that the maximum flow depth and the maximum run-up increase with the average slip on the source, while the strike of the fault is not a critical factor as Huelva is significantly far away from the potential sources identified up to now. We also show that the maximum flow depth within the inundated area is very dependent on the tidal level, while maximum run-up is less affected, as a consequence of the complex morphology of the area.

<i>Objective:</i> To investigate the association between four polymorphisms of the 5-HT_2A receptor and 5-HT transporter genes and heroin dependence. <i>Methods:</i> 113 heroin- dependent patients (DSM-IV criteria) and 420 unrelated healthy controls from Asturias (Northern Spain) were genotyped using standard methods. <i>Results:</i> There was an apparent difference in the distribution of genotypes for A-1438G polymorphisms (p = 0.024, not significant after Bonferroni correction). The 5-HT_2A -1438A allele was significantly more common in patients than controls [0.55 and 0.45, respectively; corrected p = 0.042, OR = 1.51 (95% CI = 1.13–2.03)]. An interaction was observed between A-1438G of 5-HT_2A and 5-HTT polymorphisms. The association between the -1438AA vs. AG/GG genotypes and heroin dependence was enhanced in the presence of 12-repeat 5-HTT VNTR and short 5-HTTLPR alleles [24.8% in heroin-dependent patients vs. 12.6% in controls; corrected p = 0.045, OR = 2.28 (95% CI = 1.36–3.82)]. <i>Conclusions:</i> Our findings support a contribution of the 5-HT_2A gene to susceptibility to heroin dependence, as well as a possible synergistic effect of 5-HT_2A and 5-HTT genes on susceptibility to heroin dependence.

Abstract. El Salvador is the smallest and most densely populated country in Central America; its coast has an approximate length of 320 km, 29 municipalities and more than 700 000 inhabitants. In El Salvador there were 15 recorded tsunamis between 1859 and 2012, 3 of them causing damages and resulting in hundreds of victims. Hazard assessment is commonly based on propagation numerical models for earthquake-generated tsunamis and can be approached through both probabilistic and deterministic methods. A deterministic approximation has been applied in this study as it provides essential information for coastal planning and management. The objective of the research was twofold: on the one hand the characterization of the threat over the entire coast of El Salvador, and on the other the computation of flooding maps for the three main localities of the Salvadorian coast. For the latter we developed high-resolution flooding models. For the former, due to the extension of the coastal area, we computed maximum elevation maps, and from the elevation in the near shore we computed an estimation of the run-up and the flooded area using empirical relations. We have considered local sources located in the Middle America Trench, characterized seismotectonically, and distant sources in the rest of Pacific Basin, using historical and recent earthquakes and tsunamis. We used a hybrid finite differences–finite volumes numerical model in this work, based on the linear and non-linear shallow water equations, to simulate a total of 24 earthquake-generated tsunami scenarios. Our results show that at the western Salvadorian coast, run-up values higher than 5 m are common, while in the eastern area, approximately from La Libertad to the Gulf of Fonseca, the run-up values are lower. The more exposed areas to flooding are the lowlands in the Lempa River delta and the Barra de Santiago Western Plains. The results of the empirical approximation used for the whole country are similar to the results obtained with the high-resolution numerical modelling, being a good and fast approximation to obtain preliminary tsunami hazard estimations. In Acajutla and La Libertad, both important tourism centres being actively developed, flooding depths between 2 and 4 m are frequent, accompanied with high and very high person instability hazard. Inside the Gulf of Fonseca the impact of the waves is almost negligible.

Abstract. Recently acquired swath-bathymetry data and high-resolution seismic reflection profiles offshore Adra (Almería, Spain) reveal the surficial expression of a NW–SE trending 20 km-long fault, which we termed the Adra Fault. Seismic imaging across the structure depicts a sub-vertical fault reaching the seafloor surface and slightly dipping to the NE showing an along-axis structural variability. Our new data suggest normal displacement of the uppermost units with probably a lateral component. Radiocarbon dating of a gravity core located in the area indicates that seafloor sediments are of Holocene age, suggesting present-day tectonic activity. The NE Alboran Sea area is characterized by significant low-magnitude earthquakes and by historical records of moderate magnitude, such as the Mw = 6.1 1910 Adra Earthquake. The location, dimension and kinematics of the Adra Fault agree with the fault solution and magnitude of the 1910 Adra Earthquake, whose moment tensor analysis indicates normal-dextral motion. The fault seismic parameters indicate that the Adra Fault is a potential source of large magnitude (Mw ≤ 6.5) earthquakes, which represents an unreported seismic hazard for the neighbouring coastal areas.