The Pristine survey -- XXIII. Data Release 1 and an all-sky metallicity catalogue based on Gaia DR3 BP/RP spectro-photometry

We use the spectro-photometric information of ~219 million stars from Gaia's DR3 to calculate synthetic, narrow-band, metallicity-sensitive CaHK magnitudes that mimic the observations of the Pristine survey, a survey of photometric metallicities of Milky Way stars that has been mapping more than 6,500 deg^2 of the northern sky with the CFHT since 2015. These synthetic magnitudes are used for an absolute re-calibration of the deeper Pristine photometry and, combined with broadband Gaia information, synthetic and Pristine CaHK magnitudes are used to estimate photometric metallicities over the whole sky. The resulting metallicity catalogue is accurate down to [Fe/H]~-3.5 and is particularly suited for the exploration of the metal-poor Milky Way ([Fe/H]<-1.0). We make available here the catalogue of synthetic CaHK_syn magnitudes for all stars with BP/RP information in Gaia DR3, as well as an associated catalogue of more than ~30 million photometric metallicities for high S/N FGK stars. This paper further provides the first public DR of the Pristine catalogue in the form of higher quality recalibrated Pristine CaHK magnitudes and photometric metallicities for all stars in common with the BP/RP information in Gaia DR3. We demonstrate that, when available, the much deeper Pristine data greatly enhances the quality of the derived metallicities, in particular at the faint end of the catalogue (G_BP>16). Combined, both catalogues include more than 2 million metal-poor star candidates as well as more than 200,000 and ~8,000 very and extremely metal-poor candidates. Finally, we show that these metallicity catalogues can be used efficiently, among other applications, for Galactic archaeology, to hunt for the most metal-poor stars, and to study how the structure of the Milky Way varies with metallicity, from the flat distribution of disk stars to the spheroid-shaped metal-poor halo. (Shortened)Comment: 30 pages, 24 figures, submitted to A&A. First two authors are co-first author. The CaHK photometry catalogue and the two photometric metallicity catalogues are available, before acceptance, as large compressed csv files at: https://seafile.unistra.fr/d/ee0c0f05719d4368bcbb

Mutation D816V Alters the Internal Structure and Dynamics of c-KIT Receptor Cytoplasmic Region: Implications for Dimerization and Activation Mechanisms

The type III receptor tyrosine kinase (RTK) KIT plays a crucial role in the transmission of cellular signals through phosphorylation events that are associated with a switching of the protein conformation between inactive and active states. D816V KIT mutation is associated with various pathologies including mastocytosis and cancers. D816V-mutated KIT is constitutively active, and resistant to treatment with the anti-cancer drug Imatinib. To elucidate the activating molecular mechanism of this mutation, we applied a multi-approach procedure combining molecular dynamics (MD) simulations, normal modes analysis (NMA) and binding site prediction. Multiple 50-ns MD simulations of wild-type KIT and its mutant D816V were recorded using the inactive auto-inhibited structure of the protein, characteristic of type III RTKs. Computed free energy differences enabled us to quantify the impact of D816V on protein stability in the inactive state. We evidenced a local structural alteration of the activation loop (A-loop) upon mutation, and a long-range structural re-organization of the juxta-membrane region (JMR) followed by a weakening of the interaction network with the kinase domain. A thorough normal mode analysis of several MD conformations led to a plausible molecular rationale to propose that JMR is able to depart its auto-inhibitory position more easily in the mutant than in wild-type KIT and is thus able to promote kinase mutant dimerization without the need for extra-cellular ligand binding. Pocket detection at the surface of NMA-displaced conformations finally revealed that detachment of JMR from the kinase domain in the mutant was sufficient to open an access to the catalytic and substrate binding sites

Combining μXANES and μXRD mapping to analyse the heterogeneity in calcium carbonate granules excreted by the earthworm Lumbricus terrestris

The use of fluorescence full spectral micro-X-ray absorption near-edge structure (μXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (μXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, μXRD and μXANES, probe different sample volumes but there is good agreement in the phase maps produced

Facile synthesis of branched poly(methyl methacrylate)s

Soluble, branched methyl methacrylate copolymers have been prepared via facile, one-step, batch solution free-radical polymerisations taken to high conversion. Methyl methacrylate has been copolymerised with the brancher, ethylene glycol dimethacrylate, using a chain transfer agent to inhibit gelation. Soluble branched copolymers containing unreacted double bonds have been produced and characterised by SEC and H-1 NMR spectroscopy. It has been shown that the level of branching depends on the monomer concentration, the monomer/chain transfer agent feed ratio and the conversion. It appears that branching arises through the reaction of one vinyl group of the brancher to produce polymer chains containing pendent double bonds in the first instance, followed by the reaction of the unreacted pendent double bonds with additional monomer units or other growing chains

Synthesis of branched poly(methyl methacrylate)s: Effect of the branching comonomer structure

Branched poly(methyl methacrylate)s have been prepared using conventional solution phase free radical polymerization of methyl methacrylate (MATA) in the presence of a branching divinyl comonomer with appropriate levels of dodecanethiol (DDT) chain transfer agent added to inhibit gelation. The branching comonomers employed were five ethylene glycol dimethacrylates with varying lengths of PEG chains, divinylbenzene (DVB), and ethylene glycol diacrylate (EGDA). Soluble branched polymers were obtained in good yield with a MMA/brancher mole ratio up to 100/15. The minimum mole ratio of DDT required to avoid gelation was evaluated. The isolated polymers were characterized by elemental analysis to determine the level of DDT incorporated, by H-1 NMR spectroscopy, to determine the molecular composition and in particular the level of brancher incorporated (both as a branch unit and as a pendant functionality), and by double detection SEC in order to evaluate the level of branching. The differing behaviors of the branchers are discussed with a focus on a comparison of ethylene glycol dimethacrylate (EGDMA), EGDA and DVB. The latter brancher has been shown to produce the most regularly branched material with the smallest molar mass distributions. In general, however, the latter are broad or very broad

Synthesis of branched poly(methyl methacrylate)s via controlled/living polymerisations exploiting ethylene glycol dimethacrylate as branching agent

With appropriate choice of reaction composition and conditions, copolymerisation of methyl methacrylate and ethylene glycol dimethacrylate using Cu-based ATRP or GTP methodologies yields soluble branched polymers in facile one-pot reactions

A New Radio Frequency Plasma Oxygen Primary Ion Source on Nano Secondary Ion Mass Spectrometry for Improved Lateral Resolution and Detection of Electropositive Elements at Single Cell Level

An important application field of secondary ion mass spectrometry at the nanometer scale (NanoSIMS) is the detection of chemical elements and, in particular, metals at the subcellular level in biological samples. The detection of many trace metals requires an oxygen primary ion source to allow the generation of positive secondary ions with high yield in the NanoSIMS. The duoplasmatron oxygen source is commonly used in this ion microprobe but cannot achieve the same quality of images as the cesium primary ion source used to produce negative secondary ions (C-, CN-, S-, P-) due to a larger primary ion beam size. In this paper, a new type of an oxygen ion source using a rf plasma is fitted and characterized on a NanoSIMS50L. The performances of this primary ion source in terms of current density and achievable lateral resolution have been characterized and compared to the conventional duoplasmatron and cesium sources. The new rf plasma oxygen source offered a net improvement in terms of primary beam current density compared to the commonly used duoplasmatron source, which resulted in higher ultimate lateral resolutions down to 37 nm and which provided a 5-45 times higher apparent sensitivity for electropositive elements. Other advantages include a better long-term stability and reduced maintenance. This new rf plasma oxygen primary ion source has been applied to the localization of essential macroelements and trace metals at basal levels in two biological models, cells of Chlamydomonas reinhardtii and Arabidopsis thaliana. © 2016 American Chemical Society

Chemical bioimaging for the subcellular localization of trace elements by high contrast TEM, TEM/X-EDS, and NanoSIMS

International audienceChemical bioimaging offers an important contribution to the investigation of biochemical functions, biosorption and bioaccumulation processes of trace elements via their localization at the cellular and even at the subcellular level. This paper describes the combined use of high contrast transmission electron microscopy (HC-TEM), energy dispersive X-ray spectroscopy (X-EDS), and nano secondary ion mass spectrometry (NanoSIMS) applied to a model organism, the unicellular green algae Chlamydomonas reinhardtii. HC-TEM providing a lateral resolution of 1 nm was used for imaging the ultrastructure of algae cells which have diameters of 5–10 μm. TEM coupled to X-EDS (TEM/X-EDS) combined textural (morphology and size) analysis with detection of Ca, P, K, Mg, Fe, and Zn in selected subcellular granules using an X-EDS probe size of approx. 1 μm. However, instrumental sensitivity was at the limit for trace element detection. NanoSIMS allowed chemical imaging of macro and trace elements with subcellular resolution (element mapping). Ca, Mg, and P as well as the trace elements Fe, Cu, and Zn present at basal levels were detected in pyrenoids, contractile vacuoles, and granules. Some metals were even localized in small vesicles of about 200 nm size. Sensitive subcellular localization of trace metals was possible by the application of a recently developed RF plasma oxygen primary ion source on NanoSIMS which has shown good improvements in terms of lateral resolution (below 50 nm), sensitivity, and stability. Furthermore correlative single cell imaging was developed combining the advantages of TEM and NanoSIMS. An advanced sample preparation protocol provided adjacent ultramicrotome sections for parallel TEM and NanoSIMS analyses of the same cell. Thus, the C. reinhardtii cellular ultrastructure could be directly related to the spatial distribution of metals in different cell organelles such as vacuoles and chloroplast. © 2016 Elsevier Gmb