d8···d10 RhI···AuI Interactions in Rh 2,6-Xylylisocyanide Complexes with [Au(CN)2]: Bond Analysis and Crystal Effects

Producción CientíficaThe well known [RhL4]n(anion)n structures, with RhI···RhI d8···d8 interactions, are replaced by others with RhI···AuI d8···d10 interactions such as [{RhL4}{Au(CN)2}] (L = 2,6-Xylylisocyanide) or [{RhL4}{Au(CN)2} {RhL4}{Au2(CN)3}·4(CHCl3)]∞ when the anion is [Au(CN)2]–. Orbital (Rh···Au), coulombic, and inter-unit π-π aryl stacking interactions stabilize these crystal structures.Ministerio de Economía, Industria y Competitividad (grant CTQ2017-89217-P)Junta de Castilla y León (project VA038G18

O teste do marshmallow em contexto: como o ambiente social influencia a tomada de decisões e o autocontrole?

This article proposes a discussion of psychosocial factors that influence how humans make decisions related to self-control, emphasizing how preschoolers make those decisions in delayed reward situations. To this end, it takes as a starting point the marshmallow test placed in social context, to analyze how aspects such as rationality, emotions, socioeconomic status, culture and particularly trust in others influence how decisions are made and how self-control is exercised in relation to the delay of immediate rewards to obtain, subsequently, more beneficial results.Este artículo propone una discusión sobre los factores psicosociales que influyen en la manera en que los seres humanos toman decisiones relacionadas con el autocontrol, enfatizando en la forma en que lo hacen los niños preescolares en situaciones de postergación de recompensas. Para ello, toma como punto de partida el test de la golosina puesto en contexto social, para analizar la forma en la cual aspectos tales como la racionalidad, las emociones, la condición socioeconómica y particularmente la confianza en los demás influyen en cómo se toman decisiones y cómo se ejerce o no el autocontrol en relación con el postergar recompensas inmediatas para obtener, posteriormente, otras mayores.Este artigo propõe uma discussão sobre os fatores psicossociais que influenciam a maneira em que os seres humanos tomam decisões relacionadas ao autocontrole, enfatizando o que fazem as crianças pré-escolares em situações de adiamento de recompensa. Para isso, tomamos como ponto de partida o teste do marshmallow aplicado ao contexto social, para analisar a forma pela qual aspectos como a racionalidade, as emoções, a condição socioeconômica, e particularmente a confiança nos outros influenciam em como as decisões são tomadas e como se exerce ou não o autocontrole em relação ao adiamento de recompensas imediatas para obter, posteriormente, outras maiores

Vulnerability of Catalan (NW Mediterranean) ports to wave overtopping due to different scenarios of sea level rise

The final publication is available at Springer via http://dx.doi.org/10.1007/s10113-015-0879-xThe overtopping of port breakwaters may affect the assets located at the breakwater lee side. If adaptation measures are not taken, the sea level rise will increase the overtopping discharges putting those assets at significant risk. This study compares, at a regional scale, overtopping discharges over port breakwaters for three storm conditions (return periods of 1, 5 and 50 years) under present climate as well as for three scenarios of sea level rise based on recent projections. The results indicate that, for the worst storm and sea level rise conditions, the overtopping discharge would not be negligible (larger than 1 l/s/m) in 35 ports (84 %), in contrast to only 18 ports (42 %) being affected under present conditions. In addition, in 28 ports (65 %) the overtopping would be at least one order of magnitude larger than for present conditions. In the case of large storms, in 2 ports the overtopping discharge exceeds 200 l/s/m (the discharge that can initiate breakwater damage) under present conditions, while in the worst scenario of sea level rise the number of ports exceeding this value would be 7. On the other hand, the vulnerability of each port for which overtopping flow is greater than an acceptable discharge flux is assessed, and regional maps of vulnerability are plotted. For the worst storm conditions, 23 % of the Catalan ports have risks associated with overtopping under present climate conditions. This percentage would increase to 47 % in the worst sea level rise scenario.Peer ReviewedPostprint (author's final draft

Delay of Gratification in Costa Rican Preschoolers: Effect of Trust in the Experimenter and the Socio-Economic Status: Postergación de la gratificación en preescolares costarricenses: efecto de la confianza en el experimentador y el estatus socioeconómico

This study analyzed the effect of confidence in the experimenter on the performance of a group of Costa Rican preschoolers on self-control. In addition, the effect of socioeconomic status on performance on the marshmallow task was analyzed by a comparison of children from both different schools (public vs private) and different socioeconomic contexts within each school. The sample of participants was 67 children (26 girls, M of age = 63 months, SD = 6.03). Effects were found, both of the confidence in the experimenter and of the socio-economic status in self-control. The implications of this study for future studies with children and families are discussed.Este estudio analizó el efecto de la confianza en la persona experimentadora sobre el desempeño de un grupo de niñas(os) preescolares costarricenses en el autocontrol. Adicionalmente, se analizó el efecto del estatus socioeconómico en el desempeño en la tarea de la golosina por medio de una comparación de niños provenientes tanto de diferentes escuelas (pública vs privada) como de distintos contextos socioeconómicos al interior de cada escuela. La muestra de participantes fue de 67 niños(as) (26 niñas, M de edad = 63 meses, D.T. = 6.03). Se encontraron efectos, tanto de la confianza en la persona experimentadora, como del contexto socioeconómico en el autocontrol. Se discuten las implicaciones de este estudio para futuros trabajos con niñas y niños, y familias

4-Pyridylisocyanide Gold(I) and Gold(I)-plus-Silver(I) Luminescent and Mechanochromic Materials: The Silver Role

Producción CientíficaCrystallographic and DFT examination of the metalloligands [AuAr(CNPy-4)] (Ar = C6F5 (1), C6F3Cl2-3,5 (2)) and their silver complexes [Ag[AuAr(CNPy-4)]2](BF4) (3 and 4) support that the marked luminescence red-shifts observed on moving from 1 to 2, from 1,2 to 3,4, or upon grinding, are not caused by electronic differences (either by changing the aryls C6F5/C6F3Cl2, or by N coordination to silver), nor by non-existent Au···Ag interactions. They are always due to structural changes disturbing stronger π-π stackings in order to allow for shorter Au···Au interactions.Ministerio de Economía, Industria y Competitividad (grant CTQ2017-89217-P )Junta de Castilla y León (project VA038G18

A review of potential physical impacts on harbours in the Mediterranean Sea under climate change

The final publication is available at Springer via http://dx.doi.org/10.1007/s10113-016-0972-9The potential impact of climate change on port operations and infrastructures has received much less attention than the corresponding impact for beach systems. However, ports have always been vulnerable to weather extremes and climate change could enhance such occurrences at timescales comparable to the design lifetime of harbour engineering structures. The analysis in this paper starts with the main climatic variables affecting harbour engineering and exploitation. It continues with a review of the available projections for such variables first at global scale and then at a regional scale (Catalan coast in the western Mediterranean) as a study case for similar environments in the planet. The detailed assessment of impacts starts from downscaled projections for mean sea level and wave storms (wind not considered in the paper). This is followed by an analysis of the port operations and infrastructure performance that are relevant from a climate perspective. The key climatic factors here considered are relative sea level, wave storm features (height, period, direction and duration) and their combined effect, which is expected to produce the highest impacts. The paper ends with a discussion and some examples of analyses aiming at port adaptation to future climate change.Peer ReviewedPostprint (author's final draft

Green measures for Mediterranean harbours under a changing climate

Harbour operability may be hampered by climate change. Green solutions can be used to provide extra flexibility with respect to present grey infrastructure to adapt to, and mitigate, such functional disruptions with affordable costs. This paper assesses the performance of a green solution (a seagrass meadow) by assessing its effectiveness through numerical modelling. The analysis is carried out at two harbours that, under the present climate, are prone to wave agitation and overtopping problems. The efficiencies of different seagrass layouts are tested at both sites, by comparing the relevant hydrodynamic parameters. It is concluded that, for moderate sea level rise (SLR) rates, illustrated by the central trend of a medium scenario from the Intergovernmental Panel on Climate Change, the use of seagrass meadows would be effective enough to attenuate the impact of SLR on breakwater overtopping. In addition, the use of such measures could attenuate the increases in port agitation due to changes in wave direction caused by climate change. Nevertheless, the complexity of the interactions between hydrodynamics and seagrass would require periodic monitoring and re-evaluation to maintain acceptable risk levels, especially in case of extreme scenarios.Peer ReviewedPostprint (author's final draft

Assessment of green measures as coastal defences using numerical models

Climate change may reduce the performance and design life of “grey” coastal engineering interventions. Green solutions can be combined with present infrastructures providing extra flexibility to adapt our present beaches with affordable costs. This paper assesses the behaviour of a typology of green solutions (seagrass meadows) via numerical hydro-morphodynamic modelling for an erosive beach prone to episodic flooding, under typical Mediterranean conditions. A multivariate method for jointly assessing flooding and erosion via copulas is proposed and developed. In the considered pilot site, different layouts have been tested by analysing their efficiency and limits. It is concluded that, for moderate SLR rates (RCP 4.5. central trend), these green measures could attenuate efficiently the expected changes in marine drivers. However, the complexity of eco-hydraulic interactions on which the Nature Based Solutions depend would demand periodic monitoring and evaluation for maintaining acceptable risk levels, especially in the case of high-end scenarios.Postprint (published version

Assessment of harbour inoperability and adaptation cost due to sea level rise: application to the port of Tangier-Med (Morocco)

This paper intends to assess the potential impacts of the future SLR on the operability of berthing structures and to estimate in monetary terms the adaptation costs to it. To do this, three scenarios of SLR are considered, two corresponding to the last assessment report of IPCC (RCP4.5 and RCP8.5) and the other being a high-end scenario (HES), with a low probability of occurrence but physically possible. The research is focused on the case study of Tangier-Med port, which is considered as an economic magnet for the northern region of Morocco and the centerpiece of the government strategy for port development. The results show that the operability of the port will be affected only under the HES and from 2090 onwards. However, by 2100, in this scenario all the docks would be affected, especially the service terminal and those dedicated to containers, hydrocarbons, vehicles and general cargo, in which the percentage of inoperability could exceed 30% of the time. This would lead to traffic losses of 1.9 million TEUS and more than 22 million tons of cargo by 2100 while the adaptation costs would exceed 40 million euros (in present monetary units).The work described in this publication was funded by the European Union's Seventh Framework Programme through the grant to the budget of the Collaborative Project RISES-AM-, Contract FP7-ENV-2013-two-stage-603396. The support of the Secretaria d'Universitats i Recerca del Departament d'Economia i Coneixement de la Generalitat de Catalunya (Ref 2014SGR1253) is also acknowledged.Peer ReviewedPostprint (published version

Outcome of protease inhibitor substitution with nevirapine in HIV-1 infected children

<p>Abstract</p> <p>Background</p> <p>Protease inhibitors (PIs) have been associated with metabolic complications. There is a trend to switch to simpler therapy to improve these disturbances. We report a case-series describing the effects in metabolic abnormalities in seven HIV-infected children, previously treated with protease inhibitor (PI) after switching to nevirapine.</p> <p>Methods</p> <p>Seven children with stable PI-containing regimen and a long lasting HIV-1 RNA < 50 copies/ml were switched to nevirapine. All patients were naïve to non nucleoside reverse transcriptase inhibitor. PIs were switched to nevirapine. Preentry nucleoside reverse transcriptase inhibitors were maintained. The substitution of PIs with nevirapine was made when the patient showed hyperlipidemia or lipodystrophy or the physician and/or the patient's willingness to simplify. Clinical, laboratory data and anthropometric parameters were assessed every 3 months. Dual-energy X-Ray absorptiometry scans (DXA) was performed at baseline and at 12 months.</p> <p>Results</p> <p>Seven HIV-infected children were enrolled. Median age: 130 months (99,177). Median baseline CD4%: 32%. All had HIV-1 RNA < 50 copies/ml. Median length of preentry PI-therapy was 47 months (28, 91). Median age at the beginning of nevirapine was 120 months (99,177). Median decrease in cholesterol in 7.2 mmol/L was observed (P = 0.09), from baseline to 12 months. HDL-cholesterol increased in 5.1 mmol/L (P = 0.03) throughout the study period. No significant changes were observed in DXA with regard to body fat, but changes in total body bone mineral content and lean body content were significant. CD4% remained stable. All patients but one maintained viral load < 50 copies/ml at 12 months. The patient with virologic failure referred bad adherence. Children referred to take medication more easily.</p> <p>Conclusion</p> <p>PI substitution with nevirapine improved lipid profile in our patients, although this strategy did not show significant changes in body fat or lipodystrophy.</p