Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl2]2 in the presence of NaOH and KPF6, are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with ee’s up to 98%. Iridacycles, which are prepared in similar fashion from [IrCp*Cl2]2 are excellent catalysts for the racemisation of secondary alcohols and chlorohydrins at room temperature. This allowed the development of a new dynamic kinetic resolution of chlorohydrins to the enantiopure epoxides in up to 90% yield and 98% enantiomeric excess (ee) using a mutant of the enzyme Haloalcohol dehalogenase C and an iridacycle as racemisation catalyst.

The WACMOS-ET project, part 2 : evaluation of global terrestrial evaporation data sets

The WAter Cycle Multi-mission Observation Strategy - EvapoTranspiration (WACMOS-ET) project aims to advance the development of land evaporation estimates on global and regional scales. Its main objective is the derivation, validation, and intercomparison of a group of existing evaporation retrieval algorithms driven by a common forcing data set. Three commonly used process-based evaporation methodologies are evaluated: the Penman-Monteith algorithm behind the official Moderate Resolution Imaging Spectroradiometer (MODIS) evaporation product (PM-MOD), the Global Land Evaporation Amsterdam Model (GLEAM), and the Priestley-Taylor Jet Propulsion Laboratory model (PT-JPL). The resulting global spatiotemporal variability of evaporation, the closure of regional water budgets, and the discrete estimation of land evaporation components or sources (i.e. transpiration, interception loss, and direct soil evaporation) are investigated using river discharge data, independent global evaporation data sets and results from previous studies. In a companion article (Part 1), Michel et al. (2016) inspect the performance of these three models at local scales using measurements from eddy-covariance towers and include in the assessment the Surface Energy Balance System (SEBS) model. In agreement with Part 1, our results indicate that the Priestley and Taylor products (PT-JPL and GLEAM) perform best overall for most ecosystems and climate regimes. While all three evaporation products adequately represent the expected average geographical patterns and seasonality, there is a tendency in PM-MOD to underestimate the flux in the tropics and subtropics. Overall, results from GLEAM and PT-JPL appear more realistic when compared to surface water balances from 837 globally distributed catchments and to separate evaporation estimates from ERA-Interim and the model tree ensemble (MTE). Nonetheless, all products show large dissimilarities during conditions of water stress and drought and deficiencies in the way evaporation is partitioned into its different components. This observed inter-product variability, even when common forcing is used, suggests that caution is necessary in applying a single data set for large-scale studies in isolation. A general finding that different models perform better under different conditions highlights the potential for considering biome- or climate-specific composites of models. Nevertheless, the generation of a multi-product ensemble, with weighting based on validation analyses and uncertainty assessments, is proposed as the best way forward in our long-term goal to develop a robust observational benchmark data set of continental evaporation

ruvA Mutants that resolve Holliday junctions but do not reverse replication forks

RuvAB and RuvABC complexes catalyze branch migration and resolution of Holliday junctions (HJs) respectively. In addition to their action in the last steps of homologous recombination, they process HJs made by replication fork reversal, a reaction which occurs at inactivated replication forks by the annealing of blocked leading and lagging strand ends. RuvAB was recently proposed to bind replication forks and directly catalyze their conversion into HJs. We report here the isolation and characterization of two separation-of-function ruvA mutants that resolve HJs, based on their capacity to promote conjugational recombination and recombinational repair of UV and mitomycin C lesions, but have lost the capacity to reverse forks. In vivo and in vitro evidence indicate that the ruvA mutations affect DNA binding and the stimulation of RuvB helicase activity. This work shows that RuvA's actions at forks and at HJs can be genetically separated, and that RuvA mutants compromised for fork reversal remain fully capable of homologous recombination

Positivity of the English language

Over the last million years, human language has emerged and evolved as a fundamental instrument of social communication and semiotic representation. People use language in part to convey emotional information, leading to the central and contingent questions: (1) What is the emotional spectrum of natural language? and (2) Are natural languages neutrally, positively, or negatively biased? Here, we report that the human-perceived positivity of over 10,000 of the most frequently used English words exhibits a clear positive bias. More deeply, we characterize and quantify distributions of word positivity for four large and distinct corpora, demonstrating that their form is broadly invariant with respect to frequency of word use.Comment: Manuscript: 9 pages, 3 tables, 5 figures; Supplementary Information: 12 pages, 3 tables, 8 figure

Monitoring Cognitive and Emotional Processes Through Pupil and Cardiac Response During Dynamic Versus Logical Task

The paper deals with the links between physiological measurements and cognitive and emotional functioning. As long as the operator is a key agent in charge of complex systems, the definition of metrics able to predict his performance is a great challenge. The measurement of the physiological state is a very promising way but a very acute comprehension is required; in particular few studies compare autonomous nervous system reactivity according to specific cognitive processes during task performance and task related psychological stress is often ignored. We compared physiological parameters recorded on 24 healthy subjects facing two neuropsychological tasks: a dynamic task that require problem solving in a world that continually evolves over time and a logical task representative of cognitive processes performed by operators facing everyday problem solving. Results showed that the mean pupil diameter change was higher during the dynamic task; conversely, the heart rate was more elevated during the logical task. Finally, the systolic blood pressure seemed to be strongly sensitive to psychological stress. A better taking into account of the precise influence of a given cognitive activity and both workload and related task-induced psychological stress during task performance is a promising way to better monitor operators in complex working situations to detect mental overload or pejorative stress factor of error

An extrasolar planetary system with three Neptune-mass planets

Over the past two years, the search for low-mass extrasolar planets has led to the detection of seven so-called 'hot Neptunes' or 'super-Earths' around Sun-like stars. These planets have masses 5-20 times larger than the Earth and are mainly found on close-in orbits with periods of 2-15 days. Here we report a system of three Neptune-mass planets with periods of 8.67, 31.6 and 197 days, orbiting the nearby star HD 69830. This star was already known to show an infrared excess possibly caused by an asteroid belt within 1 AU (the Sun-Earth distance). Simulations show that the system is in a dynamically stable configuration. Theoretical calculations favour a mainly rocky composition for both inner planets, while the outer planet probably has a significant gaseous envelope surrounding its rocky/icy core; the outer planet orbits within the habitable zone of this star.Comment: 17 pages, 3 figures, preprint of the paper published in Nature on May 18, 200

Implementing cognitive behavior therapy for chronic fatigue syndrome in mental health care: a costs and outcomes analysis

Contains fulltext : 69822.pdf (publisher's version ) (Open Access

Accuracy and repeatability of wrist joint angles in boxing using an electromagnetic tracking system

© 2019, The Author(s). The hand-wrist region is reported as the most common injury site in boxing. Boxers are at risk due to the amount of wrist motions when impacting training equipment or their opponents, yet we know relatively little about these motions. This paper describes a new method for quantifying wrist motion in boxing using an electromagnetic tracking system. Surrogate testing procedure utilising a polyamide hand and forearm shape, and in vivo testing procedure utilising 29 elite boxers, were used to assess the accuracy and repeatability of the system. 2D kinematic analysis was used to calculate wrist angles using photogrammetry, whilst the data from the electromagnetic tracking system was processed with visual 3D software. The electromagnetic tracking system agreed with the video-based system (paired t tests) in both the surrogate ( 0.9). In the punch testing, for both repeated jab and hook shots, the electromagnetic tracking system showed good reliability (ICCs > 0.8) and substantial reliability (ICCs > 0.6) for flexion–extension and radial-ulnar deviation angles, respectively. The results indicate that wrist kinematics during punching activities can be measured using an electromagnetic tracking system

Improved Unsteady RANS Models Applied to Jet Transverse to a Pipe Flow

An unsteady RANS model is developed in order to simulate the complex situations involving both free and bounded flows. This model tuned to catch coherent flow structures is developed both in the k-ε and k-l approaches. The full 3D geometry of a round jet exiting from a reservoir into a pipe has been computed. Periodic conditions are applied in order to compare with an experiments consisting of eight jets exiting in a cross pipe flow. Improvement has been obtained with this URANS turbulence model compared to RANS and good agreement compared with experiments has been obtained. Unsteady phenomena are reproduced by the model and provide more insight into the physical properties of the flow and of the transport of a passive scalar