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

The dynamics of cultivation and floods in arable lands of Central Argentina

Although floods in watersheds have been associated with land-use change since ancient times, the dynamics of flooding is still incompletely understood. In this paper we explored the relations between rainfall, groundwater level, and cultivation to explain the dynamics of floods in the extremely flat and valuable arable lands of the Quinto river watershed, in central Argentina. The analysis involved an area of 12.4 million hectare during a 26-year period (1978–2003), which comprised two extensive flooding episodes in 1983–1988 and 1996–2003. Supported by information from surveys as well as field and remote sensing measurements, we explored the correlation among precipitation, groundwater levels, flooded area and land use. Flood extension was associated to the dynamics of groundwater level. While no correlation with rainfall was recorded in lowlands, a significant correlation (<i>P</i><0.01) between groundwater and rainfall in highlands was found when estimations comprise a time lag of one year. Correlations between groundwater level and flood extension were positive in all cases, but while highly significant relations (<i>P</i><0.01) were found in highlands, non significant relations (<i>P</i>>0.05) predominate in lowlands. Our analysis supports the existence of a cyclic mechanism driven by the reciprocal influence between cultivation and groundwater in highlands. This cycle would involve the following stages: (a) cultivation boosts the elevation of groundwater levels through decreased evapotranspiration; (b) as groundwater level rises, floods spread causing a decline of land cultivation; (c) flooding propitiates higher evapotranspiration favouring its own retraction; (d) cultivation expands again following the retreat of floods. Thus, cultivation would trigger a destabilizing feedback self affecting future cultivation in the highlands. It is unlikely that such sequence can work in lowlands. The results suggest that rather than responding directly and solely to the same mechanism, floods in lowlands may be the combined result of various factors like local rainfall, groundwater level fluctuations, surface and subsurface lateral flow, and water-body interlinking. Although the hypothetical mechanisms proposed here require additional understanding efforts, they suggest a promising avenue of environmental management in which cultivation could be steered in the region to smooth the undesirable impacts of floods

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

Antitumour necrosis factor-α therapy for hidradenitis suppurativa: results from a national cohort study between 2000 and 2013

International audienceHidradenitis suppurativa (HS) is a frequent chronic inflammatory skin disease typically characterized by recurrent painful, deep inflammatory nodules of the axillary, breast, groin and gluteal areas. European recommendations are mainly based on expert opinion. Drug treatments are heterogenous (e.g., antibiotics, corticosteroids, retinoids) and lack consensus among expert centres. The most severe disease forms or those failing to respond to conventional drugs may be associated with worsened functional prognosis. Anti-tumor necrosis factor α (anti-TNFα) drugs have been prescribed in these cases. The results of randomized controlled trials (RCTs) are discordant. Three RCTs concluded to the efficacy of adalimumab (ADA), and two others did not detect any difference between infliximab (IFX) or etanercept (ETA) and placebo. Finally, data from the literature and reported experiences do not conclude on the efficacy of anti-TNFα drugs for HS. This article is protected by copyright. All rights reserve

Are white storks addicted to junk food? Impacts of landfill use on the movement and behaviour of resident white storks (Ciconia ciconia) from a partially migratory population

Background: The migratory patterns of animals are changing in response to global environmental change with many species forming resident populations in areas where they were once migratory. The white stork (Ciconia ciconia) was wholly migratory in Europe but recently guaranteed, year-round food from landfill sites has facilitated the establishment of resident populations in Iberia. In this study 17 resident white storks were fitted with GPS/GSM data loggers (including accelerometer) and tracked for 9.1 ± 3.7 months to quantify the extent and consistency of landfill attendance by individuals during the non-breeding and breeding seasons and to assess the influence of landfill use on daily distances travelled, percentage of GPS fixes spent foraging and non-landfill foraging ranges. Results: Resident white storks used landfill more during non-breeding (20.1 % ± 2.3 of foraging GPS fixes) than during breeding (14.9 % ± 2.2). Landfill attendance declined with increasing distance between nest and landfill in both seasons. During non-breeding a large percentage of GPS fixes occurred on the nest throughout the day (27 % ± 3.0 of fixes) in the majority of tagged storks. This study provides first confirmation of year-round nest use by resident white storks. The percentage of GPS fixes on the nest was not influenced by the distance between nest and the landfill site. Storks travelled up to 48.2 km to visit landfills during non-breeding and a maximum of 28.1 km during breeding, notably further than previous estimates. Storks nesting close to landfill sites used landfill more and had smaller foraging ranges in non-landfill habitat indicating higher reliance on landfill. The majority of non-landfill foraging occurred around the nest and long distance trips were made specifically to visit landfill. Conclusions: The continuous availability of food resources on landfill has facilitated year-round nest use in white storks and is influencing their home ranges and movement behaviour. White storks rely on landfill sites for foraging especially during the non-breeding season when other food resources are scarcer and this artificial food supplementation probably facilitated the establishment of resident populations. The closure of landfills, as required by EU Landfill Directives, will likely cause dramatic impacts on white stork populations

A bird's eye view of discard reforms: bird-borne cameras reveal seabird/fishery interactions.

notes: PMCID: PMC3590202types: Journal Article; Research Support, Non-U.S. Gov'tCopyright: © 2013 Votier et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.Commercial capture fisheries produce huge quantities of offal, as well as undersized and unwanted catch in the form of discards. Declines in global catches and legislation to ban discarding will significantly reduce discards, but this subsidy supports a large scavenger community. Understanding the potential impact of declining discards for scavengers should feature in an eco-system based approach to fisheries management, but requires greater knowledge of scavenger/fishery interactions. Here we use bird-borne cameras, in tandem with GPS loggers, to provide a unique view of seabird/fishery interactions. 20,643 digital images (one min(-1)) from ten bird-borne cameras deployed on central place northern gannets Morus bassanus revealed that all birds photographed fishing vessels. These were large (>15 m) boats, with no small-scale vessels. Virtually all vessels were trawlers, and gannets were almost always accompanied by other scavenging birds. All individuals exhibited an Area-Restricted Search (ARS) during foraging, but only 42% of ARS were associated with fishing vessels, indicating much 'natural' foraging. The proportion of ARS behaviours associated with fishing boats were higher for males (81%) than females (30%), although the reasons for this are currently unclear. Our study illustrates that fisheries form a very important component of the prey-landscape for foraging gannets and that a discard ban, such as that proposed under reforms of the EU Common Fisheries Policy, may have a significant impact on gannet behaviour, particularly males. However, a continued reliance on 'natural' foraging suggests the ability to switch away from scavenging, but only if there is sufficient food to meet their needs in the absence of a discard subsidy.EU INTERREG project CHARM-IIINatural Environment Research CouncilAssociation for the Study of Animal Behaviour research gran

International multicentre observational study to assess the efficacy and safety of a 0·5 mg kg−1 per day starting dose of oral corticosteroids to treat bullous pemphigoid

BackgroundEuropean guidelines propose a 0 center dot 5 mg kg(-1) per day dose of oral prednisone as initial treatment for bullous pemphigoid (BP). We assessed the safety and efficacy of this regimen depending on BP extent and general condition of the patients.MethodsIn a prospective international study, we consecutively included all patients diagnosed with BP. Patients received a 0 center dot 5 mg kg(-1) per day dose of prednisone, which was then gradually tapered 15 days after disease control, with the aim of stopping prednisone or maintaining minimal treatment (0 center dot 1 mg kg(-1) per day) within 6 months after the start of treatment. The two coprimary endpoints were control of disease activity at day 21 and 1-year overall survival. Disease severity was assessed according to the Bullous Pemphigoid Disease Area Index (BPDAI) score.ResultsIn total, 198 patients were included between 2015 and 2017. The final analysis comprised 190 patients with a mean age of 80 center dot 9 (SD 9 center dot 1) years. Control of disease activity was achieved at day 21 in 119 patients [62 center dot 6%, 95% confidence interval (CI) 55 center dot 3-69.5]; 18 of 24 patients (75%, 95% CI 53 center dot 3-90 center dot 2), 75 of 110 patients (68 center dot 8%, 95% CI 59 center dot 2-77 center dot 3) and 26 of 56 patients (46.4%, 95% CI 33 center dot 0-60 center dot 3) had mild, moderate and severe BP, respectively (P = 0 center dot 0218). A total of 30 patients died during the study. The overall Kaplan-Meier 1-year survival was 82 center dot 6% (95% CI 76 center dot 3-87 center dot 4) corresponding to 90 center dot 9%, 83 center dot 0% and 80 center dot 0% rates in patients with mild, moderate and severe BP, respectively (P = 0 center dot 5). Thresholds of 49 points for BPDAI score and 70 points for Karnofsky score yielded maximal Youden index values with respect to disease control at day 21 and 1-year survival, respectively.ConclusionsA 0 center dot 5 mg kg(-1) per day dose of prednisone is a valuable therapeutic option in patients with mild or moderate BP whose general condition allows them to be autonomous.</p