(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles.

Although BH3 simply coordinates the endocyclic P of (phospholidino)phosphaketene 1Dipp , the bulkier B(C6F5)3 gives rise to a zwitterionic diphosphirenium, which is a novel type of 2π-electron aromatic system as shown by the calculated NICS values. While the reaction of 1Dipp with Na[PCO(dioxane) x ] is unselective, the same reaction with the sterically bulky (phospholidino)phosphaketene 1Ar** [Ar** = 2,6-bis[di(4-tert-butylphenyl)methyl]-4-methylphenyl selectively affords a sodium bridged dimer containing a hitherto unknown λ3,λ5,λ3-triphosphete core. The latter formally results from "P-" addition to a 1,3-P/C-dipole. Similarly, adamantyl isonitrile adds to 1Dipp giving a 4-membered phosphacycle. In contrast to 1, the phosphaketene derived from the electrophilic diazaphospholidine-4,5-dione is unstable and reacts with a second molecule of Na[PCO(dioxane) x ] to afford a 1,3,4-oxadiphospholonide derivative

Oxidation Assisted Intergranular Cracking in Alloy 718: Effects of Strain Rate and Temperature

Alloy 718 is the most widely used superalloy in industry due to its excellent mechanical properties, as well as its oxidation and corrosion resistance over a wide range of temperatures and solicitation modes. Nevertheless, it is a well-known fact that this alloy is sensitive to oxidation assisted intergranular cracking under loading in the temperature range encountered in service. The mechanisms resulting in such degradation are not well-understood, but it has been well established that a relation exists between a change in fracture mode and the apparition of plastic instability phenomena over a wide range of temperatures. Quantification and characterization of the damaging process provide important information leading to a better understanding of the degradation mechanisms involved in the oxidation assisted intergranular cracking of this alloy. These observations allow various domains to be defined in the strain rate - temperature plane, where the damaging process characteristics are different: a high strain rate / low temperature domain in which instabilities occur and where the fracture mode is systematically transgranular ductile, an intermediary domain where numerous intergranular crack initiations can be observed, and a slow strain rate / high temperature domain where crack propagation is enhanced. These results lead to the proposal of consistent scenarii to explain grain boundary opening due to applied intergranular normal stress and critical decohesion stress changes

Comportement mécanique et couplage mécanique-oxydation dans l'alliage 718 : effet des éléments en solution solide

L'alliage 718 est le superalliage le plus utilisé industriellement du fait de ses excellentes propriétés mécaniques, ainsi que de sa tenue à l'oxydation et à la corrosion dans une large gamme de températures et de modes de sollicitation. Néanmoins, cet alliage présente une sensibilité vis-àvis des phénomènes de corrosion sous contrainte et fissuration assistée par l'oxydation sous contrainte dans les gammes de température de service. Les mécanismes à l'origine de ce phénomène restent encore mal compris, cependant un lien entre le changement de mode de rupture et les domaines d'apparition d'instabilités de l'écoulement plastique est clairement établi. Au cours de cette étude nous avons étudié ce phénomène d'instabilités, effet Portevin Le Chatelier, de l'alliage 718 au cours d'essais de traction menés dans une large gamme de températures et de vitesses de déformation. Différents domaines d'instabilités ont pu être mis en évidence, dont les caractéristiques suggèrent l'interaction des dislocations avec des solutés de différentes natures : interstitiels aux plus basses températures, et substitutionnels pour les températures les plus élevées. Des essais de spectroscopie mécanique sur l'alliage 718 et des alliages de compositions voisines montrent un effet de la mobilité des atomes de molybdène au sein du matériau dans cette gamme de températures. Des essais dédiés à l'étude des phénomènes d'interaction entre plasticité et oxydation ont aussi été réalisés. Les résultats mettent en évidence un fort effet de vitesse sur les propriétés mécaniques de l'alliage 718 en atmosphère inerte et sur les caractéristiques de l'endommagement intergranulaire assisté par l'oxydation lors d'essais sous air laboratoire. La discussion engendrée par l'ensemble des résultats présentés permet d'émettre certaines hypothèses sur les couplages entre mécanismes de déformation et endommagement par l'oxydation à l'origine des phénomènes de fissuration observés. ABSTRACT : Alloy 718 is the superalloy the most widely used in industry due to its excellent mechanical properties, as well as oxidation and corrosion resistance in wide range of temperatures and solicitation modes. Nevertheless, it is a well-known fact that this alloy is sensitive to stress corrosion cracking and oxidation assisted cracking under loading in the range of temperatures met in service. Mechanisms explaining this phenomenon are not well understood: nevertheless, it is well established that a relation exists between a change in fracture mode and the apparition of plastic instabilities phenomenon. During this study, the instability phenomenon, Portevin-Le Chatelier effect, in alloy 718 was studied by tensile tests in wide ranges of temperatures and strain rates. Different domains of plastic instabilities have been evidenced. Their characteristics suggest the existence of interactions between dislocations and different types of solute elements: interstitials for lower temperatures and substitutionals for higher testing temperatures. Mechanical spectroscopy tests have been performed on alloy 718 and various alloys which composition is comparable to that of alloy 718. These tests prove the mobility of molybdenum atoms in the alloy in the studied temperature range. Specific tests have been performed to study interaction phenomenon between plasticity and oxidation. These results highlight the strong effect of plastic strain rate on both mechanical behavior and intergranular cracking in alloy 718. The subsequent discussion leads to propose hypothesis on coupling effects between deformation mechanisms and oxidation assisted embrittlement in the observed cracking processes

The strategy of antibiotic use in critically ill neutropenic patients

Suspicion of sepsis in neutropenic patients requires immediate antimicrobial treatment. The initial regimen in critically ill patients should cover both Gram-positive and Gram-negative pathogens, including Pseudomonas aeruginosa. However, the risk of selecting multidrug-resistant pathogens should be considered when using broad-spectrum antibiotics for a prolonged period of time. The choice of the first-line empirical drugs should take into account the underlying malignancy, local bacterial ecology, clinical presentation and severity of acute illness. This review provides an up-to-date guide that will assist physicians in choosing the best strategy regarding the use of antibiotics in neutropenic patients, with a special focus on critically ill patients, based on the above-mentioned considerations and on the most recent international guidelines and literature

Supervised Remote Robot with Guided Autonomy and Teleoperation (SURROGATE): A Framework for Whole-Body Manipulation

The use of the cognitive capabilities of humans to help guide the autonomy of robotics platforms in what is typically called “supervised-autonomy” is becoming more commonplace in robotics research. The work discussed in this paper presents an approach to a human-in-the-loop mode of robot operation that integrates high level human cognition and commanding with the intelligence and processing power of autonomous systems. Our framework for a “Supervised Remote Robot with Guided Autonomy and Teleoperation” (SURROGATE) is demonstrated on a robotic platform consisting of a pan-tilt perception head, two 7-DOF arms connected by a single 7-DOF torso, mounted on a tracked-wheel base. We present an architecture that allows high-level supervisory commands and intents to be specified by a user that are then interpreted by the robotic system to perform whole body manipulation tasks autonomously. We use a concept of “behaviors” to chain together sequences of “actions” for the robot to perform which is then executed real time

Synthesis, structural characterization, and chiroptical properties of planarly and axially chiral boranils

International audience2-Amino[2.2]paracyclophane reacts with salicylaldehyde or 2-hydroxyacetophenone to yield imines that then give access to a new series of boranils (8b–d) upon complexation with BF2. These novel boron-containing compounds display both planar and axial chiralities and were examined experimentally and computationally. In particular, their photophysical and chiroptical properties were studied and compared to newly prepared, simpler boranils (9a–d) exhibiting axial chirality only. Less sophisticated chiral architectures were shown to demonstrate overall stronger circularly polarized luminescence (CPL) activity

DexROV: Enabling effective dexterous ROV operations in presence of communication latency

Subsea interventions in the oil & gas industry as well as in other domains such as archaeology or geological surveys are demanding and costly activities for which robotic solutions are often deployed in addition or in substitution to human divers - contributing to risks and costs cutting. The operation of ROVs (Remotely Operated Vehicles) nevertheless requires significant off-shore dedicated manpower to handle and operate the robotic platform and the supporting vessel. In order to reduce the footprint of operations, DexROV proposes to implement and evaluate novel operation paradigms with safer, more cost effective and time efficient ROV operations. As a keystone of the proposed approach, manned support will in a large extent be delocalized within an onshore ROV control center, possibly at a large distance from the actual operations, relying on satellite communications. The proposed scheme also makes provision for advanced dexterous manipulation and semi-autonomous capabilities, leveraging human expertise when deemed useful. The outcomes of the project will be integrated and evaluated in a series of tests and evaluation campaigns, culminating with a realistic deep sea (1,300 meters) trial in the Mediterranean sea

Antimicrobial resistance among migrants in Europe: a systematic review and meta-analysis

BACKGROUND: Rates of antimicrobial resistance (AMR) are rising globally and there is concern that increased migration is contributing to the burden of antibiotic resistance in Europe. However, the effect of migration on the burden of AMR in Europe has not yet been comprehensively examined. Therefore, we did a systematic review and meta-analysis to identify and synthesise data for AMR carriage or infection in migrants to Europe to examine differences in patterns of AMR across migrant groups and in different settings. METHODS: For this systematic review and meta-analysis, we searched MEDLINE, Embase, PubMed, and Scopus with no language restrictions from Jan 1, 2000, to Jan 18, 2017, for primary data from observational studies reporting antibacterial resistance in common bacterial pathogens among migrants to 21 European Union-15 and European Economic Area countries. To be eligible for inclusion, studies had to report data on carriage or infection with laboratory-confirmed antibiotic-resistant organisms in migrant populations. We extracted data from eligible studies and assessed quality using piloted, standardised forms. We did not examine drug resistance in tuberculosis and excluded articles solely reporting on this parameter. We also excluded articles in which migrant status was determined by ethnicity, country of birth of participants' parents, or was not defined, and articles in which data were not disaggregated by migrant status. Outcomes were carriage of or infection with antibiotic-resistant organisms. We used random-effects models to calculate the pooled prevalence of each outcome. The study protocol is registered with PROSPERO, number CRD42016043681. FINDINGS: We identified 2274 articles, of which 23 observational studies reporting on antibiotic resistance in 2319 migrants were included. The pooled prevalence of any AMR carriage or AMR infection in migrants was 25·4% (95% CI 19·1-31·8; I2 =98%), including meticillin-resistant Staphylococcus aureus (7·8%, 4·8-10·7; I2 =92%) and antibiotic-resistant Gram-negative bacteria (27·2%, 17·6-36·8; I2 =94%). The pooled prevalence of any AMR carriage or infection was higher in refugees and asylum seekers (33·0%, 18·3-47·6; I2 =98%) than in other migrant groups (6·6%, 1·8-11·3; I2 =92%). The pooled prevalence of antibiotic-resistant organisms was slightly higher in high-migrant community settings (33·1%, 11·1-55·1; I2 =96%) than in migrants in hospitals (24·3%, 16·1-32·6; I2 =98%). We did not find evidence of high rates of transmission of AMR from migrant to host populations. INTERPRETATION: Migrants are exposed to conditions favouring the emergence of drug resistance during transit and in host countries in Europe. Increased antibiotic resistance among refugees and asylum seekers and in high-migrant community settings (such as refugee camps and detention facilities) highlights the need for improved living conditions, access to health care, and initiatives to facilitate detection of and appropriate high-quality treatment for antibiotic-resistant infections during transit and in host countries. Protocols for the prevention and control of infection and for antibiotic surveillance need to be integrated in all aspects of health care, which should be accessible for all migrant groups, and should target determinants of AMR before, during, and after migration. FUNDING: UK National Institute for Health Research Imperial Biomedical Research Centre, Imperial College Healthcare Charity, the Wellcome Trust, and UK National Institute for Health Research Health Protection Research Unit in Healthcare-associated Infections and Antimictobial Resistance at Imperial College London

A Re-examination of the Portevin-Le Chatelier Effect in Alloy 718 in Connection with Oxidation-Assisted Intergranular Cracking

In Alloy 718, a sharp transition exists in the fracture path changing from an intergranular brittle mode to a transgranular ductile mode which is associated with a transition of flow behavior from smooth in the dynamic strain aging regime to a serrated one in the Portevin-Le Chatelier (PLC) regime. In order to better understand both deformation and rupture behavior, PLC phenomenon in a precipitation-hardened nickel-base superalloy was carefully investigated in a wide range of temperatures [573 K to 973 K (300°C to 700°C)] and strain rates (109^-5 to 3.2910^-2 s^-1 ). Distinction was made between two PLC domains characterized by different evolutions of the critical strain to the onset of the first serration namely normal and inverse behavior. The apparent activation energies associated with both domains were determined using different methods. Results showed that normal and inverse behavior domains are related to dynamic interaction of dislocations with, respectively, interstitial and substitutional solutes atoms. This analysis confirms that normal PLC regime may be associated to the diffusion of carbon atoms, whereas the substitutional species involves in the inverse regime is discussed with an emphasis on the role of Nb and Mo

The North American Multi-Model Ensemble (NMME): Phase-1 Seasonal to Interannual Prediction, Phase-2 Toward Developing Intra-Seasonal Prediction

The recent US National Academies report "Assessment of Intraseasonal to Interannual Climate Prediction and Predictability" was unequivocal in recommending the need for the development of a North American Multi-Model Ensemble (NMME) operational predictive capability. Indeed, this effort is required to meet the specific tailored regional prediction and decision support needs of a large community of climate information users. The multi-model ensemble approach has proven extremely effective at quantifying prediction uncertainty due to uncertainty in model formulation, and has proven to produce better prediction quality (on average) then any single model ensemble. This multi-model approach is the basis for several international collaborative prediction research efforts, an operational European system and there are numerous examples of how this multi-model ensemble approach yields superior forecasts compared to any single model. Based on two NOAA Climate Test Bed (CTB) NMME workshops (February 18, and April 8, 2011) a collaborative and coordinated implementation strategy for a NMME prediction system has been developed and is currently delivering real-time seasonal-to-interannual predictions on the NOAA Climate Prediction Center (CPC) operational schedule. The hindcast and real-time prediction data is readily available (e.g., http://iridl.ldeo.columbia.edu/SOURCES/.Models/.NMME/) and in graphical format from CPC (http://origin.cpc.ncep.noaa.gov/products/people/wd51yf/NMME/index.html). Moreover, the NMME forecast are already currently being used as guidance for operational forecasters. This paper describes the new NMME effort, presents an overview of the multi-model forecast quality, and the complementary skill associated with individual models