FALCON: a concept to extend adaptive optics corrections to cosmological fields

FALCON is an original concept for a next generation spectrograph at ESO VLT or at future ELTs. It is a spectrograph including multiple small integral field units (IFUs) which can be deployed within a large field of view such as that of VLT/GIRAFFE. In FALCON, each IFU features an adaptive optics correction using off-axis natural reference stars in order to combine, in the 0.8-1.8 \mu m wavelength range, spatial and spectral resolutions (0.1-0.15 arcsec and R=10000+/-5000). These conditions are ideally suited for distant galaxy studies, which should be done within fields of view larger than the galaxy clustering scales (4-9 Mpc), i.e. foV > 100 arcmin2. Instead of compensating the whole field, the adaptive correction will be performed locally on each IFU. This implies to use small miniaturized devices both for adaptive optics correction and wavefront sensing. Applications to high latitude fields imply to use atmospheric tomography because the stars required for wavefront sensing will be in most of the cases far outside the isoplanatic patch.Comment: To appear in the Backaskog "Second Workshop on ELT" SPIE proceeding

Electronic Properties of Poly-Yne Carbon Chains and Derivatives with Transition Metal End-Groups

International audienceDuring the last three decades, experimental chemists have forged a plethora of bimetallic molecular wires in which two redox-active metal termini are linked by a carbon-rich bridge. Their extensive redox chemistry with multiple, stepwise, one-electron oxidation processes provide them with some interesting electronic and/or magnetic properties for potential applications. The nature of both the metal end-groups and the carbon bridge has a significant effect on the redox process, which is of paramount importance for the design of these systems. Indeed, examples of mono-oxidized complexes range from weakly coupled mixed-valence species through more strongly coupled systems in which the bridging ligand can be intimately involved in electron transfer processes. Similarly, di-oxidized species can encompass difference in magnetic behavior depending upon not only the nature of the framework of the systems but also the torsion angle between the terminal spin carriers, which allows the inversion of the singlet vs. triplet ground states. Theoretical quantum chemical computations have greatly assisted the development of this field of research. This review illustrates how, in synergy with experiments, computational results can provide additional valuable information on the nature of the localized vs. delocalized electronic communication in the mono-oxidized mixed-valence species, or the magnetic coupling differences and characteristics of the di-oxidized complexes

Synthesis and Properties of a Mixed-​Valence Compound with Single-​Step Tunneling and Multiple-​Step Hopping Behavior

International audienceThe org. precursor bis(trimethylsilylethynyl)​TTFMe2 (3, TTF = tetrathiafulvalene) was prepd. as a 1:1 mixt. of the cis and trans isomers. Pure samples of 3-​cis and 3-​trans were obtained by crystn. and identified by XRD anal. The treatment of pure 3-​trans and a 1:1 mixt. of 3-​cis​/trans with (i) potassium carbonate, (ii) the iron complex Cp*(dppe)​FeCl [5, Cp* = η5-​C5Me5, dppe = 1,​2-​bis(diphenylphosphanyl)​ethane] in the presence of KPF6, and (iii) tBuOK provided Cp*(dppe)​Fe-​C C-​TTFMe2-​C C-​Fe(dppe)​Cp* as the pure geometric isomer 6-​trans (85 %) and as the 60:40 mixt. 6-​cis​/trans (63 %)​, resp. The oxidn. of 6-​trans with [(C5H5)​2Fe]​PF6 gave [6-​trans]​[PF6]​n (n = 1-​3)​. Visible, IR, near-​IR (NIR)​, and ESR (EPR) spectroscopy together with DFT data show that [6-​trans]​[PF6] is a class II mixed-​valence complex (Hab = 85 cm-​1) in which the spin distribution depends on the conformation of the mol. Intramol. electron transfer occurs through single-​step tunneling and a multistep hoping mechanism. The triplet state is thermally accessible for [6-​trans]​[PF6]​2

Hybrid molecular systems containing tetrathiafulvalene and iron-alkynyl electrophores : five-component functional molecules obtained from C-H bond activation.

International audienceTreatment of [Cp*(dppe)Fe-C≡C-TTFMe3] (1) with Ag[PF6] (3 equiv) in DMF provides the binuclear complex [Cp*(dppe)Fe=C=C=TTFMe2 =CH-CH=TTFMe2 =C=C=Fe(dppe)Cp*][PF6]2 (2[PF6 ]2) isolated as a deep-blue powder in 69 % yield. EPR monitoring of the reaction and comparison of the experimental and calculated EPR spectra allowed the identification of the radical salt [Cp*(dppe)Fe=C=C=TTFMe2 =CH][PF6]2 ([1-CH][PF6]) an intermediate of the reaction, which results from the activation of the methyl group attached in vicinal position with respect to the alkynyl-iron on the TTF ligand by the triple oxidation of 1 leading to its deprotonation by the solvent. The dimerization of [1-CH][PF6] through carbon-carbon bond formation provides 2[PF6]2. The cyclic voltammetry (CV) experiments show that 2[PF6]2 is subject to two sequential well-reversible one-electron reductions yielding the complexes 2[PF6] and 2. The CV also shows that further oxidation of 2[PF6]2 generates 2[PF6]n (n=3-6) at the electrode. Treatment of 2[PF6]2 with KOtBu provides 2[PF6] and 2 as stable powders. The salts 2[PF6] and 2[PF6]2 were characterized by XRD. The electronic structures of 2(n+) (n=0-2) were computed. The new complexes were also characterized by NMR, IR, Mössbauer, EPR, UV/Vis and NIR spectroscopies. The data show that the three complexes 2[PF6]n are iron(II) derivatives in the ground state. In the solid state, the dication 2(2+) is diamagnetic and has a bis(allenylidene-iron) structure with one positive charge on each iron building block. In solution, as a result of the thermal motion of the metal-carbon backbone, the triplet excited state becomes thermally accessible and equilibrium takes place between singlet and triplet states. In 2[PF6], the charge and the spin are both symmetrically distributed on the carbon bridge and only moderately on the iron and TTFMe2 electroactive centers

Chiral supramolecular nanotubes of single-chain magnets

International audienceWe report a Single-Chain Magnet (SCM) made of a Terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44% porosity. Ab-initio calculations highlight that each Tb III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc = 2400 Oe MR = 2.09 µB at 0.5 K) for this class of compounds

Upregulation of BST-2 by type i interferons reduces the capacity of Vpu to protect HIV-1-infected cells from NK cell responses

The restriction factor BST-2 and the NK cell ligands NTB-A and PVR are among a growing list of membrane proteins found to be downregulated by HIV-1 Vpu. BST-2 antagonism enhances viral release, while NTB-A and PVR downmodulation contributes to NK cell evasion. However, it remains unclear how Vpu can target multiple cellular factors simultaneously. Here we provide evidence that under physiological conditions, BST-2 is preferentially targeted by Vpu over NTB-A and PVR. Specifically, we show that type I IFNs decrease Vpu’s polyfunctionality by upregulating BST-2, thus reducing its capacity to protect HIV-1-infected cells from NK cell responses. This indicates that there is a hierarchy of Vpu substrates upon IFN treatment, revealing that for the virus, targeting BST-2 as part of its resistance to IFN takes precedence over evading NK cell responses. This reveals a potential weakness in HIV-1’s immunoevasion mechanisms that may be exploited therapeutically to harness NK cell responses against HIV-1.The HIV-1 accessory protein Vpu enhances viral release by counteracting the restriction factor BST-2. Furthermore, Vpu promotes NK cell evasion by downmodulating cell surface NTB-A and PVR, known ligands of the NK cell receptors NTB-A and DNAM-1, respectively. While it has been established that Vpu’s transmembrane domain (TMD) is required for the interaction and intracellular sequestration of BST-2, NTB-A, and PVR, it remains unclear how Vpu manages to target these proteins simultaneously. In this study, we show that upon upregulation, BST-2 is preferentially downregulated by Vpu over its other TMD substrates. We found that type I interferon (IFN)-mediated BST-2 upregulation greatly impairs the ability of Vpu to downregulate NTB-A and PVR. Our results suggest that occupation of Vpu by BST-2 affects its ability to downregulate other TMD substrates. Accordingly, knockdown of BST-2 increases Vpu’s potency to downmodulate NTB-A and PVR in the presence of type I IFN treatment. Moreover, we show that expression of human BST-2, but not that of the macaque orthologue, decreases Vpu’s capacity to downregulate NTB-A. Importantly, we show that type I IFNs efficiently sensitize HIV-1-infected cells to NTB-A- and DNAM-1-mediated direct and antibody-dependent NK cell responses. Altogether, our results reveal that type I IFNs decrease Vpu’s polyfunctionality, thus reducing its capacity to protect HIV-1-infected cells from NK cell responses

Barth syndrome: cellular compensation of mitochondrial dysfunction and apoptosis inhibition due to changes in cardiolipin remodeling linked to tafazzin (TAZ) gene mutation

Cardiolipin is a mitochondrion-specific phospholipid that stabilizes the assembly of respiratory chain complexes, favoring full-yield operation. It also mediates key steps in apoptosis. In Barth syndrome, an X chromosome-linked cardiomyopathy caused by tafazzin mutations, cardiolipins display acyl chain modifications and are present at abnormally low concentrations, whereas monolysocardiolipin accumulates. Using immortalized lymphoblasts from Barth syndrome patients, we showed that the production of abnormal cardiolipin led to mitochondrial alterations. Indeed, the lack of normal cardiolipin led to changes in electron transport chain stability, resulting in cellular defects. We found a destabilization of the supercomplex (respirasome) I + III2 + IVn but also decreased amounts of individual complexes I and IV and supercomplexes I + III and III + IV. No changes were observed in the amounts of individual complex III and complex II. We also found decreased levels of complex V. This complex is not part of the supercomplex suggesting that cardiolipin is required not only for the association/stabilization of the complexes into supercomplexes but also for the modulation of the amount of individual respiratory chain complexes. However, these alterations were compensated by an increase in mitochondrial mass, as demonstrated by electron microscopy and measurements of citrate synthase activity. We suggest that this compensatory increase in mitochondrial content prevents a decrease in mitochondrial respiration and ATP synthesis in the cells. We also show, by extensive flow cytometry analysis, that the type II apoptosis pathway was blocked at the mitochondrial level and that the mitochondria of patients with Barth syndrome cannot bind active caspase-8. Signal transduction is thus blocked before any mitochondrial event can occur. Remarkably, basal levels of superoxide anion production were slightly higher in patients' cells than in control cells as previously evidenced via an increased protein carbonylation in the taz1Δ mutant in the yeast. This may be deleterious to cells in the long term. The consequences of mitochondrial dysfunction and alterations to apoptosis signal transduction are considered in light of the potential for the development of future treatments

Improving constraints on the extended mass distribution in the Galactic Center with stellar orbits

International audienceStudying the orbital motion of stars around Sagittarius A* in the Galactic Center provides a unique opportunity to probe the gravitational potential near the supermassive black hole at the heart of our Galaxy. Interferometric data obtained with the GRAVITY instrument at the Very Large Telescope Interferometer (VLTI) since 2016 has allowed us to achieve unprecedented precision in tracking the orbits of these stars. GRAVITY data have been key to detecting the in-plane, prograde Schwarzschild precession of the orbit of the star S2, as predicted by General Relativity. By combining astrometric and spectroscopic data from multiple stars, including S2, S29, S38, and S55 - for which we have data around their time of pericenter passage with GRAVITY - we can now strengthen the significance of this detection to an approximately $10 \sigma$ confidence level. The prograde precession of S2's orbit provides valuable insights into the potential presence of an extended mass distribution surrounding Sagittarius A*, which could consist of a dynamically relaxed stellar cusp comprised of old stars and stellar remnants, along with a possible dark matter spike. Our analysis, based on two plausible density profiles - a power-law and a Plummer profile - constrains the enclosed mass within the orbit of S2 to be consistent with zero, establishing an upper limit of approximately $1200 \, M_\odot$ with a $1 \sigma$ confidence level. This significantly improves our constraints on the mass distribution in the Galactic Center. Our upper limit is very close to the expected value from numerical simulations for a stellar cusp in the Galactic Center, leaving little room for a significant enhancement of dark matter density near Sagittarius A*