Sulfonylative Hiyama Cross-Coupling: Development and Mechanistic Insights

International audienceDue to distinctive structural and electronic features, sulfones have attracted a particular attention over the pa st few decades, ma king it a widespread functional group.[1] Present in many contemporary pharmaceuticals and agrochemicals, they are also used as essential intermediates in organic synthesis. Therefore, numérous methodologies have been developed for their preparation. [1] However, the most common methods suffer from significant limitations with harsh reaction conditions or regioselectivity issues. Recently, the insertion of a molecule of sulfur dioxide between two partners was investigated and reactions involving organomagnesium,[2a] organozind2b] and organoboron[2c] compounds were reported. Herein we report a direct single-step palladium-catalyzed synthesis of sulfones involving organosilanes, sulfur dioxide and organohalides. Different mechanistic pathways were envisaged and discussed both from an experimental and theoretical stand point

Guidance in author instructions of hematology and oncology journals: A cross sectional and longitudinal study.

The debate about the value of biomedical publications led to recommendations for improving reporting quality. It is unclear to what extent these recommendations have been endorsed by journals. We analyzed whether specific recommendations were included in author instructions, which journal characteristics were associated with their endorsement, how endorsement of the domains changed and whether endorsement was associated with change of impact factor between 2010 and 2015. We considered two study samples consisting of "Hematology" and "Oncology" journals of the Journal Citation Report 2008 and 2014, respectively. We extracted information regarding endorsement of the (1) recommendations of the International Committee of Medical Journal Editors, of (2) reporting guidelines, (3) requirement for trial registration and (4) disclosure of conflicts of interest. Data extraction was done by reading the author instructions before conducting a text search with keywords. We calculated a global generalized linear mixed effects model for endorsement of each of the four domains followed by separate multivariable logistic regression models and a longitudinal analysis. We defined endorsement as the author instructions saying that they approve the use of the recommendations. In 2015, the ICMJE recommendations were mentioned in author instructions of 156 journals (67.5%). CONSORT was referred to by 77 journals (33.3%); MOOSE, PRISMA, STARD and STROBE were referred to by less than 15% of journals. There were 99 journals (42.9%) that recommended or required trial registration, 211 (91.3%) required authors to disclose conflicts of interest. Journal impact factor, journal start year and geographical region were positively associated with endorsement of any of the four domains. The overall endorsement of all domains increased between 2010 and 2015. The endorsement of any domain in 2010 seemed to be associated with an increased impact factor in 2014. Hematology and oncology journals endorse major recommendations to various degrees. Endorsement is increasing slowly over time and might be positively associated with the journals' impact factor

Retrieval of Snow Water Equivalent by the Precipitation Imaging Package (PIP) in the Northern Great Lakes

Performance of the Precipitation Imaging Package (PIP) for estimating the snow water equivalent (SWE) is evaluated through a comparative study with the collocated National Oceanic and Atmospheric Administration National Weather Service snow stake field measurements. The PIP together with a vertically pointing radar, a weighing bucket gauge, and a laser-optical disdrometer was deployed at the NWS Marquette, Michigan, office building for a long-term field study supported by the National Aeronautics and Space Administration's Global Precipitation Measurement mission Ground Validation program. The site was also equipped with a weather station. During the 2017/18 winter, the PIP functioned nearly uninterrupted at frigid temperatures accumulating 2345.8 mm of geometric snow depth over a total of 499 h. This long record consists of 30 events, and the PIP-retrieved and snow stake field measured SWE differed less than 15% in every event. Two of the major events with the longest duration and the highest accumulation are examined in detail. The particle mass with a given diameter was much lower during a shallow, colder, uniform lake-effect event than in the deep, less cold, and variable synoptic event. This study demonstrated that the PIP is a robust instrument for operational use, and is reliable for deriving the bulk properties of falling snow.Peer reviewe

Zero-variance principle for Monte Carlo algorithms

We present a general approach to greatly increase at little cost the efficiency of Monte Carlo algorithms. To each observable to be computed we associate a renormalized observable (improved estimator) having the same average but a different variance. By writing down the zero-variance condition a fundamental equation determining the optimal choice for the renormalized observable is derived (zero-variance principle for each observable separately). We show, with several examples including classical and quantum Monte Carlo calculations, that the method can be very powerful.Comment: 9 pages, Latex, to appear in Phys. Rev. Let

Cluster update and recognition

We present a fast and robust cluster update algorithm that is especially efficient in implementing the task of image segmentation using the method of superparamagnetic clustering. We apply it to a Potts model with spin interactions that are are defined by gray-scale differences within the image. Motivated by biological systems, we introduce the concept of neural inhibition to the Potts model realization of the segmentation problem. Including the inhibition term in the Hamiltonian results in enhanced contrast and thereby significantly improves segmentation quality. As a second benefit we can - after equilibration - directly identify the image segments as the clusters formed by the clustering algorithm. To construct a new spin configuration the algorithm performs the standard steps of (1) forming clusters and of (2) updating the spins in a cluster simultaneously. As opposed to standard algorithms, however, we share the interaction energy between the two steps. Thus the update probabilities are not independent of the interaction energies. As a consequence, we observe an acceleration of the relaxation by a factor of 10 compared to the Swendson and Wang procedure.Comment: 4 pages, 2 figure

Infrared behavior of the gluon propagator in lattice Landau gauge: the three-dimensional case

We evaluate numerically the three-momentum-space gluon propagator in the lattice Landau gauge, for three-dimensional pure-SU(2) lattice gauge theory with periodic boundary conditions. Simulations are done for nine different values of the coupling $\beta$, from $\beta = 0$ (strong coupling) to $\beta = 6.0$ (in the scaling region), and for lattice sizes up to $V = 64^3$. In the limit of large lattice volume we observe, in all cases, a gluon propagator decreasing for momenta smaller than a constant value $p_{dec}$. From our data we estimate $p_{dec} \approx 350$ MeV. The result of a gluon propagator decreasing in the infrared limit has a straightforward interpretation as resulting from the proximity of the so-called first Gribov horizon in the infrared directions.Comment: 14 pages, BI-TP 99/03 preprint, correction in the Acknowledgments section. To appear in Phys.Rev.

The Precipitation Imaging Package : Assessment of Microphysical and Bulk Characteristics of Snow

Remote-sensing observations are needed to estimate the regional and global impacts of snow. However, to retrieve accurate estimates of snow mass and rate, these observations require augmentation through additional information and assumptions about hydrometeor properties. The Precipitation Imaging Package (PIP) provides information about precipitation characteristics and can be utilized to improve estimates of snowfall rate and accumulation. Here, the goal is to demonstrate the quality and utility of two higher-order PIP-derived products: liquid water equivalent snow rate and an approximation of volume-weighted density called equivalent density. Accuracy of the PIP snow rate and equivalent density is obtained through intercomparison with established retrieval methods and through evaluation with colocated ground-based observations. The results confirm the ability of the PIP-derived products to quantify properties of snow rate and equivalent density, and demonstrate that the PIP produces physically realistic snow characteristics. When compared to the National Weather Service (NWS) snow field measurements of six-hourly accumulation, the PIP-derived accumulations were biased only +2.48% higher. Additionally, this work illustrates fundamentally different microphysical and bulk features of low and high snow-to-liquid ratio events, through assessment of observed particle size distributions, retrieved mass coefficients, and bulk properties. Importantly, this research establishes the role that PIP observations and higher-order products can serve for constraining microphysical assumptions in ground-based and spaceborne remotely sensed snowfall retrievals.Peer reviewe

The VLT-FLAMES survey of massive stars: constraints on stellar evolution from the chemical compositions of rapidly rotating Galactic and Magellanic Cloud B-type stars

We have previously analysed the spectra of 135 early B-type stars in the LMC and found several groups of stars that have chemical compositions that conflict with the theory of rotational mixing. Here we extend this study to Galactic and SMC metallicities with the analysis of ~50 Galactic and ~100 SMC early B-type stars with rotational velocities up to ~300km/s. The surface nitrogen abundances are utilised as a probe of the mixing process. In the SMC, we find a population of slowly rotating nitrogen-rich stars amongst the early B type core-hydrogen burning stars, similar to the LMC. In the Galactic sample we find no significant enrichment amongst the core hydrogen-burning stars, which appears to be in contrast with the expectation from both rotating single-star and close binary evolution models. However, only a small number of the rapidly rotating stars have evolved enough to produce a significant nitrogen enrichment, and these may be analogous to the non-enriched rapid rotators previously found in the LMC sample. Finally, in each metallicity regime, a population of highly enriched supergiants is observed, which cannot be the immediate descendants of core-hydrogen burning stars. Their abundances are, however, compatible with them having gone through a previous red supergiant phase. Together, these observations paint a complex picture of the nitrogen enrichment in massive main sequence and supergiant stellar atmospheres, where age and binarity cause crucial effects. Whether rotational mixing is required to understand our results remains an open question at this time, but could be answered by identifying the true binary fraction in those groups of stars that do not agree with single-star evolutionary models (abridged).Comment: Accepted paper - 86 pages with tables and figure

Practical recommendations for fertility preservation in women by the FertiPROTEKT network. Part I: Indications for fertility preservation.

PURPOSE Most guidelines about fertility preservation are predominantly focused on scientific evidence, but are less practically orientated. Therefore, practically oriented recommendations are needed to support the clinician in daily practice. METHODS A selective literature search was performed based on the clinical and scientific experience of the authors, focussing on the most relevant diseases and gynaecological cancers. This article (Part I) provides information on topics that are essential for the fertility preservation indication, such as disease prognosis, disease therapy and its associated risks to fertility, recommending disease-specific fertility preservation measures. Part II specifically focusses on fertility preservation techniques. RESULTS In breast cancer patients, fertility preservation such as ovarian tissue and oocyte cryopreservation is especially recommended in low-stage cancer and in women < 35 years of age. In Hodgkin's lymphoma, the indication is mainly based on the chemotherapy regime as some therapies have very low, others very high gonadotoxicity. In borderline ovarian tumours, preservation of fertility usually is achieved through fertility sparing surgery, ovarian stimulation may also be considered. In cervical cancer, endometrial cancer, rheumatic diseases and other malignancies such as Ewing sarcoma, colorectal carcinoma, non-Hodgkin lymphoma, leukaemia etc., several other factors must be considered to enable an individual, stage-dependent decision. CONCLUSION The decision for or against fertility preservation depends on the prognosis, the risks to fertility and individual factors such as prospective family planning

SU(2) Landau gluon propagator on a 140^3 lattice

We present a numerical study of the gluon propagator in lattice Landau gauge for three-dimensional pure-SU(2) lattice gauge theory at couplings beta = 4.2, 5.0, 6.0 and for lattice volumes V = 40^3, 80^3, 140^3. In the limit of large V we observe a decreasing gluon propagator for momenta smaller than p_{dec} = 350^{+ 100}_{- 50} MeV. Data are well fitted by Gribov-like formulae and seem to indicate an infra-red critical exponent kappa slightly above 0.6, in agreement with recent analytic results.Comment: 5 pages with 2 figures and 3 tables; added a paragraph on discretization effect