Chiral transition-metal complexes as Brønsted-acid catalysts for the asymmetric Friedel-Crafts hydroxyalkylation of indoles.

The Friedel-Crafts reaction between 3,3,3-trifluoropyruvates and indoles is efficiently catalysed by the iridium complex [(η5-C 5Me5)Ir{(R)-Prophos}(H2O)][SbF 6]2 (1) with up to 84% ee. Experimental data and theoretical calculations support a mechanism involving the Brønsted-acid activation of the pyruvate carbonyl by the protons of the coordinated water molecule in 1. Water is not dissociated during the process and, therefore, the catalytic reaction occurs with no direct interaction between the substrates and the metal. This journal is © the Partner Organisations 2014.The authors acknowledge the Ministerio de Economía y Competitividad (MINECO, Grants CTQ2006-03030/BQU, CTQ2009-10303/BQU, CTQ2011-27033 and Consolider Ingenio 2010 CSD2006-003), Gobierno de Aragón (Grupo Consolidado: Catálisis Homogénea Enantioselectiva), Generalitat de Catalunya (2009SGR0259) and the ICIQ foundation for financial support. A. S. and R. R. acknowledge MINECO for predoctoral fellowships. S. D.-G. acknowledges MINECO for a “Torres Quevedo” contract.Peer Reviewe

Simulación de procesos con controladores lógico-programables (PLC’s)

La realización de prácticas en el laboratorio de control de procesos presenta como mayor dificultad el coste asociado al funcionamiento del proceso, debido al consumo de reactivos, de energía o a la generación de residuos. Por tanto se propone trabajar con un proceso simulado en un controlador lógico- programable o PLC, con lo que se realiza una práctica de bajo coste y más cercana a la realidad que la pura simulación numérica

Isotopic carbon analysis of meteoritic organic matter

Isotopic carbon analysis of meteoritic organic matte

Fish associated with floating drifting objects as a feeding resource for Balearic Shearwaters Puffinus mauretanicus during the breeding season

Publicado

Asymmetric 1,3-dipolar cycloaddition reactions between enals and nitrones catalysed by half-sandwich rhodium or iridium diphosphane complexes

The aqua complexes ¿(¿5-C5Me5)M¿PP*)¿H2O)]¿SbF6]2 (M = Rh, Ir; PP* = chiral diphosphane) have been tested as catalysts for the asymmetric 1,3-dipolar cycloaddition of nitrones to a,ß-unsaturated aldehydes. Quantitative conversions with very high regioselectivity, perfect endo selectivity and excellent enantioselectivity (up to 99% ee) were achieved. The stereochemical outcome was analyzed on the basis of the stereoelectronic properties of the intermediate enal complexes of the formula ¿(¿5-C5Me5)M¿PP*)¿enal)]¿SbF6]2

Predator arrival elicits differential dispersal, change in age structure and reproductive performance in a prey population

Acknowledgements We thank everyone monitoring colonies over the years, in particular Carles Domingo from the Ebro Delta NP Staff, Ràpita, Castelló and the Tarragona Port Authorities and José Manuel Igual from the Group of Ecology and Animal Demography. We also thank the editorial board and the reviewers for their constructive comments. RESET (ref.CGL2017-85210-P), FPU (ref. FPU2012-000869), IBISES (ref. CGL2013-42203-R) and MINOW (ref. H2020- 634495). ASA and MG are supported by a postdoctoral contract co-funded by the Regional Government of the Balearic Islands and the European Social Fund (ref. PD/003/2016 and PD/023/2015).Peer reviewedPublisher PD

c-FOS drives reversible basal to squamous cell carcinoma transition.

While squamous transdifferentiation within subpopulations of adenocarcinomas represents an important drug resistance problem, its underlying mechanism remains poorly understood. Here, using surface markers of resistant basal cell carcinomas (BCCs) and patient single-cell and bulk transcriptomic data, we uncover the dynamic roadmap of basal to squamous cell carcinoma transition (BST). Experimentally induced BST identifies activator protein 1 (AP-1) family members in regulating tumor plasticity, and we show that c-FOS plays a central role in BST by regulating the accessibility of distinct AP-1 regulatory elements. Remarkably, despite prominent changes in cell morphology and BST marker expression, we show using inducible model systems that c-FOS-mediated BST demonstrates reversibility. Blocking EGFR pathway activation after c-FOS induction partially reverts BST in vitro and prevents BST features in both mouse models and human tumors. Thus, by identifying the molecular basis of BST, our work reveals a therapeutic opportunity targeting plasticity as a mechanism of tumor resistance

Estimating the cumulative effects of the nature-based tourism in a coastal dolphin population from southern Kenya

Due to the growth of nature-based tourism worldwide, behavioural studies are needed to assess the impact of this industry on wildlife populations and understand their short-term effect. Tourism impact on dolphin populations remain poorly documented in developing countries. This study investigates the effects of nature-based tourism on the behaviour of the Indo-Pacific bottlenose dolphins (Tursiops aduncus) in southern Kenya. We used Markov chain models to estimate transition probabilities between behavioural states in the presence and absence of tourist boats, and assess the overall behavioural budgets. Based on these data and the tourism intensity in the area, we quantified the potential tourist boat disturbance over the period 2006-2013. Our results demonstrated that tourist boat interactions affected dolphins' behavioural budgets, with a significant decrease in the overall amount of time travelling and an increase in diving. The average duration of travelling and resting decreased significantly in the presence of boats. Although the cumulative tourism exposure was not significant for the dolphin population at their current levels, these impacts should be taken into consideration with the potential tourism growth in the area. This is particularly important if tourism reaches periods of high intensity, as we have shown that these periods could have a significant impact for the species, particularly where home-range and core areas are highly overlap by this activity. Understanding the effect of human disturbance variations from previous years may help to predict the consequences on dolphin populations, towards achieving a more ecological and economic sustainability of the activity

Use of the Richtmyer-Meshkov Instability to Infer Yield Stress at High-Energy Densities

We use the Richtmyer-Meshkov instability (RMI) at a metal-gas interface to infer the metal’s yield stress (Y) under shock loading and release. We first model how Y stabilizes the RMI using hydrodynamics simulations with a perfectly plastic constitutive relation for copper (Cu). The model is then tested with molecular dynamics (MD) of crystalline Cu by comparing the inferred Y from RMI simulations with direct stress-strain calculations, both with MD at the same conditions. Finally, new RMI experiments with solid Cu validate our simulation-based model and infer Y~0.47 GPa for a 36 GPa shock