Délégation Alpes

Abstract We report the results from the first 5D tomographic diffraction imaging experiment of a complex Ni–Pd/CeO 2 –ZrO 2 /Al 2 O 3 catalyst used for methane reforming. This five-dimensional (three spatial, one scattering and one dimension to denote time/imposed state) approach enabled us to track the chemical evolution of many particles across the catalyst bed and relate these changes to the gas environment that the particles experience. Rietveld analysis of some 2 × 10 6 diffraction patterns allowed us to extract heterogeneities in the catalyst from the Å to the nm and to the μm scale (3D maps corresponding to unit cell lattice parameters, crystallite sizes and phase distribution maps respectively) under different chemical environments. We are able to capture the evolution of the Ni-containing species and gain a more complete insight into the multiple roles of the CeO 2 -ZrO 2 promoters and the reasons behind the partial deactivation of the catalyst during partial oxidation of methane.

Primordial black holes (pbhs) have motivated many studies since it was shown that they should evaporate and produce all kinds of particles (Hawking [CITE]). Recent experimental measurements of cosmic rays with great accuracy, theoretical investigations on the possible formation mechanisms and detailed evaporation processes have revived the interest in such astrophysical objects. This article aims to use the latest developments in antiproton propagation models (Maurin et al. [CITE]; Donato et al. [CITE]) together with new data from BESS, CAPRICE and AMS experiments to constrain the local amount of pbh dark matter. Depending on the diffusion halo parameters and on the details of the emission mechanisms, we derive an average upper limit of the order of g cm-3.

The vacuolar protein sorting 4 AAA-ATPase (Vps4) recycles endosomal sorting complexes required for transport (ESCRT-III) polymers from cellular membranes. Here we present a 3.6-Å X-ray structure of ring-shaped Vps4 from Metallosphera sedula (MsVps4), seen as an asymmetric pseudohexamer. Conserved key interface residues are shown to be important for MsVps4 assembly, ATPase activity in vitro, ESCRT-III disassembly in vitro and HIV-1 budding. ADP binding leads to conformational changes within the protomer, which might propagate within the ring structure. All ATP-binding sites are accessible and the pseudohexamer binds six ATP with micromolar affinity in vitro. In contrast, ADP occupies one high-affinity and five low-affinity binding sites in vitro, consistent with conformational asymmetry induced on ATP hydrolysis. The structure represents a snapshot of an assembled Vps4 conformation and provides insight into the molecular motions the ring structure undergoes in a concerted action to couple ATP hydrolysis to ESCRT-III substrate disassembly.

Primordial black holes (PBHs) have motivated many studies since it was shown that they should evaporate and produce all kinds of particles. Recent experimental measurements of cosmic rays with great accuracy, theoretical investigations on the possible formation mechanisms and detailed evaporation processes have revived the interest in such astrophysical objects. This article aims at using the latest developments on antiproton propagation models together with new data from BESS, CAPRICE and AMS experiments to constrain the local amount of PBH dark matter. Depending on the diffusion halo parameters and on the details of emission mechanism, we derive an average upper limit of the order of rho < 1.7E-33 g cm^-3.

Rapid shape changes are observed for neutron-rich nuclei with A around 100. In particular, a sudden onset of ground-state deformation is observed in the Zr and Sr isotopic chains at N = 60: Low-lying states in $N\ensuremath{\le}58$ nuclei are nearly spherical, while those with $N\ensuremath{\ge}60$ have a rotational character. Nuclear lifetimes as short as a few picoseconds can be measured using fast-timing techniques with ${\mathrm{LaBr}}_{3}$(Ce) scintillators, yielding a key ingredient in the systematic study of the shape evolution in this region. We used neutron-induced fission of $^{241}\mathrm{Pu}$ and $^{235}\mathrm{U}$ to study lifetimes of excited states in fission fragments in the $A\ensuremath{\sim}100$ region with the EXILL-FATIMA array located at the PF1B cold neutron beam line at the Institut Laue-Langevin. In particular, we applied the generalized centroid difference method to deduce lifetimes of low-lying states for the nuclei $^{98}\mathrm{Zr}$ (N = 58), $^{100}\mathrm{Zr}$, and $^{102}\mathrm{Zr}$ ($N\ensuremath{\ge}60$). The results are discussed in the context of the presumed phase transition in the Zr chain by comparing the experimental transition strengths with the theoretical calculations using the interacting boson model and the Monte Carlo shell model.

Abstract Cadmium yellows (CdYs) refer to a family of cadmium sulfide pigments, which have been widely used by artists since the late 19th century. Despite being considered stable, they are suffering from discoloration in iconic paintings, such as Joy of Life by Matisse, Flowers in a blue vase by Van Gogh, and The Scream by Munch, most likely due to the formation of CdSO 4 ⋅ n H 2 O. The driving factors of the CdYs degradation and how these affect the overall process are still unknown. Here, we study a series of oil mock‐up paints made of CdYs of different stoichiometry (CdS/Cd 0.76 Zn 0.24 S) and crystalline structure (hexagonal/cubic) before and after aging at variable relative humidity under exposure to light and in darkness. Synchrotron radiation‐based X‐ray methods combined with UV‐Vis and FTIR spectroscopy show that: 1) Cd 0.76 Zn 0.24 S is more susceptible to photooxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. 2) The photooxidation of CdS/Cd 0.76 Zn 0.24 S to CdSO 4 ⋅ n H 2 O is triggered by moisture. 3) The nature of alteration products depends on the aging conditions and the Cd/Zn stoichiometry. Based on our findings, we propose a scheme for the mechanism of the photocorrosion process and the photocatalytic activity of CdY pigments in the oil binder. Overall, our results form a reliable basis for understanding the degradation of CdS‐based paints in artworks and contribute towards developing better ways of preserving them for future generations.

Abstract The reaction processes in Li‐ion batteries can be highly heterogeneous at the electrode scale, leading to local deviations in the lithium content or local degradation phenomena. To access the distribution of lithiated phases throughout a high energy density silicon‐graphite composite anode, correlative operando SAXS and WAXS tomography are applied. In‐plane and out‐of‐plane inhomogeneities are resolved during cycling at moderate rates, as well as during relaxation steps performed at open circuit voltage at given states of charge. Lithium concentration gradients in the silicon phase are formed during cycling, with regions close to the current collector being less lithiated when charging. In relaxing conditions, the multi‐phase and multi‐scale heterogeneities vanish to equilibrate the chemical potential. In particular, Li‐poor silicon regions pump lithium ions from both lithiated graphite and Li‐rich silicon regions. This charge redistribution between active materials is governed by distinct potential homogenization throughout the electrode and hysteretic behaviors. Such intrinsic concentration gradients and out‐of‐equilibrium charge dynamics, which depend on electrode and cell state of charge, must be considered to model the durability of high capacity Li‐ion batteries.

It is well established that the formation of transthyretin (TTR) amyloid fibrils is linked to the destabilization and dissociation of its tetrameric structure into insoluble aggregates. Isotope labeling is used for the study of TTR by NMR, neutron diffraction, and mass spectrometry (MS). Here MS, thioflavin T fluorescence, and crystallographic data demonstrate that while the X-ray structures of unlabeled and deuterium-labeled TTR are essentially identical, subunit exchange kinetics and amyloid formation are accelerated for the deuterated protein. However, a slower subunit exchange is noted in deuterated solvent, reflecting the poorer solubility of non-polar protein side chains in such an environment. These observations are important for the interpretation of kinetic studies involving deuteration. The destabilizing effects of TTR deuteration are rather similar in character to those observed for aggressive mutations of TTR such as L55P (associated with familial amyloid polyneuropathy).

In most cosmological models, primordial black holes (pbh) should have formed in the early Universe. Their Hawking evaporation into particles could eventually lead to the formation of antideuterium nuclei. This paper is devoted to a first computation of this antideuteron flux. The production of these antinuclei is studied with a simple coalescence scheme, and their propagation in the Galaxy is treated with a well-constrained diffusion model. We compare the resulting primary flux to the secondary background, due to the spallation of protons on the interstellar matter. Antideuterons are shown to be a very sensitive probe for primordial black holes in our Galaxy. The next generation of experiments should allow investigators to significantly improve the current upper limit, nor even provide the first evidence of the existence of evaporating black holes.

Abstract The P21/a to A2/a transition in titanite has been studied at high pressure (and room temperature) by X-ray powder diffraction. On the basis of the disappearance of k + l= odd reflections from the diffraction pattern, the transition was located between 3·351(3) and 3·587(3) GPa. The variation with pressure of the spontaneous strain in the P21/a phase indicates that the transition has an effective critical exponent significantly less than 1/2. Within the uncertainties of the data, the transition could be weakly first-order in character or be continuous with an effective critical exponent in the range of ∼0·13-0·25. The A2/a to P21/a transition is accompanied by a significant expansion of the a-axis as a result of the bond-valence sum requirements of the Ti atoms: in the high-pressure phase they occupy the centres of the TiO6 octahedra, but they are displaced along the a-axis in the P21/a phase to form alternating short and long Ti-O bonds.

International audience

Resonant ultrasound spectroscopy (RUS) is the state-of-the-art method used to investigate the elastic properties of anisotropic solids. Recently, RUS was applied to measure human cortical bone, an anisotropic material with low Q-factor (20), which is challenging due to the difficulty in retrieving resonant frequencies. Determining the precision of the estimated stiffness constants is not straightforward because RUS is an indirect method involving minimizing the distance between measured and calculated resonant frequencies using a model. This work was motivated by the need to quantify the errors on stiffness constants due to different error sources in RUS, including uncertainties on the resonant frequencies and specimen dimensions and imperfect rectangular parallelepiped (RP) specimen geometry. The errors were first investigated using Monte Carlo simulations with typical uncertainty values of experimentally measured resonant frequencies and dimensions assuming a perfect RP geometry. Second, the exact specimen geometry of a set of bone specimens were recorded by synchrotron radiation micro-computed tomography. Then, a "virtual" RUS experiment is proposed to quantify the errors induced by imperfect geometry. Results show that for a bone specimen of ∼1° perpendicularity and parallelism errors, an accuracy of a few percent ( <6.2%) for all the stiffness constants and engineering moduli is achievable.

International audience

Abstract In many ferroelectrics, large electromechanical strains are observed near regions of composition- or temperature- driven phase coexistence. Phenomenologically, this is attributed to easy re-orientation of the polarization vector and/or phase transition, although their effects are highly convoluted and difficult to distinguish experimentally. Here, we used synchrotron X-ray scattering and digital image correlation to differentiate between the microscopic mechanisms leading to large electrostrains in an exemplary Pb-free piezoceramic Sn-doped barium calcium zirconate titanate. Large electrostrains of ~0.2% measured at room-temperature are attributed to an unconventional effect, wherein polarization switching is aided by a reversible phase transition near the tetragonal-orthorhombic phase boundary. Additionally, electrostrains of ~0.1% or more could be maintained from room temperature to 140 °C due to a succession of different microscopic mechanisms. In situ X-ray diffraction elucidates that while 90° domain reorientation is pertinent below the Curie temperature ( T C ), isotropic distortion of polar clusters is the dominant mechanism above T C .

In this report we show for the first time that neutron anomalous dispersion can be used in a practical manner to determine experimental phases of a protein crystal structure, providing a new tool for structural biologists. The approach is demonstrated through the use of a state-of-the-art monochromatic neutron diffractometer at the Institut Laue-Langevin (ILL) in combination with crystals of perdeuterated protein that minimise the level of hydrogen incoherent scattering and enhance the visibility of the anomalous signal. The protein used was rubredoxin in which cadmium replaced the iron at the iron-sulphur site. While this study was carried out using a steady-state neutron beam source, the results will be of major interest for capabilities at existing and emerging spallation neutron sources where time-of-flight instruments provide inherent energy discrimination. In particular this capability may be expected to offer unique opportunities to a rapidly developing structural biology community where there is increasing interest in the identification of protonation states, protein/water interactions and protein-ligand interactions - all of which are of central importance to a wide range of fundamental and applied areas in the biosciences.

Synchrotron X-rays on the Swiss Norwegian Beamline and BM28 (XMaS) at the ESRF have been used to record the diffraction response of the PMN–PT relaxor piezoelectric 67% Pb(Mg 1/3 Nb 2/3 )O 3 –33% PbTiO 3 as a function of externally applied electric field. A DC field in the range 0–18 kV cm −1 was applied along the [001] pseudo-cubic direction using a specially designed sample cell for in situ single-crystal diffraction experiments. The cell allowed data to be collected on a Pilatus 2M area detector in a large volume of reciprocal space using transmission geometry. The data showed good agreement with a twinned single-phase monoclinic structure model. The results from the area detector were compared with previous Bragg peak mapping using variable electric fields and a single detector where the structural model was ambiguous. The coverage of a significantly larger section of reciprocal space facilitated by the area detector allowed precise phase analysis.

Prion diseases, a group of incurable, lethal neurodegenerative disorders of mammals including humans, are caused by prions, assemblies of misfolded host prion protein (PrP). A single point mutation (G127V) in human PrP prevents prion disease, however the structural basis for its protective effect remains unknown. Here we show that the mutation alters and constrains the PrP backbone conformation preceding the PrP β-sheet, stabilising PrP dimer interactions by increasing intermolecular hydrogen bonding. It also markedly changes the solution dynamics of the β2-α2 loop, a region of PrP structure implicated in prion transmission and cross-species susceptibility. Both of these structural changes may affect access to protein conformers susceptible to prion formation and explain its profound effect on prion disease.

Chemical condensation of layers of silicates has been often proposed as an alternative to thermal condensation, finding limited success. The formation of the industrially relevant MCM-22 zeolite (MWW IZA code) from a mild hydrothermal precursor is the most important example of 2D-3D aluminosilicate condensation. Silanols of opposed layers have been condensed by acid-driven dehydration in concentrated nitric acid, as confirmed by powder XRD and 29Si NMR spectroscopy, implying interlayer template extraction and corresponding dealumination. Milder acid treatments favour template extraction and shrinkage of interlayer distance, but do not provide significant silanol condensation. Template extraction is further favoured by degradation of the organics in the presence of a Cu2+ homogeneous catalyst.

Abstract It is well established that the formation of transthyretin (TTR) amyloid fibrils is linked to the destabilization and dissociation of its tetrameric structure into insoluble aggregates. Isotope labeling is used for the study of TTR by NMR, neutron diffraction, and mass spectrometry (MS). Here MS, thioflavin T fluorescence, and crystallographic data demonstrate that while the X‐ray structures of unlabeled and deuterium‐labeled TTR are essentially identical, subunit exchange kinetics and amyloid formation are accelerated for the deuterated protein. However, a slower subunit exchange is noted in deuterated solvent, reflecting the poorer solubility of non‐polar protein side chains in such an environment. These observations are important for the interpretation of kinetic studies involving deuteration. The destabilizing effects of TTR deuteration are rather similar in character to those observed for aggressive mutations of TTR such as L55P (associated with familial amyloid polyneuropathy).

Since 2001, the SPIRAL 1 facility has been one of the pioneering facilities in ISOL techniques for re-accelerating radioactive ion beams: the fragmentation of the heavy ion beams of GANIL on graphite targets and subsequent ionization in the Nanogan ECR ion source has permitted to deliver beams of gaseous elements (He, N, O, F, Ne, Ar, Kr) to numerous experiments. Thanks to the CIME cyclotron, energies up to 20 AMeV could be obtained. In 2014, the facility was stopped to undertake a major upgrade, with the aim to extend the production capabilities of SPIRAL 1 to a number of new elements. This upgrade, which is presently under commissioning, consists in the integration of an ECR booster in the SPIRAL 1 beam line to charge breed the beam of different 1+ sources. A FEBIAD source (the so-called VADIS from ISOLDE) was chosen to be the future workhorse for producing many metallic ion beams. This source was coupled to the SPIRAL 1 graphite targets and tested on-line with different beams at GANIL. The charge breeder is an upgraded version of the Phoenix booster which was previously tested in ISOLDE. It was recently commissioned at LPSC and lately in the SPIRAL 1 beam lines with stable beams. The upgrade additionally permits the use of other target material than graphite. In particular, the use of fragmentation targets will permit to produce higher intensities than from projectile fragmentation, and thin targets of high Z will be used for producing beams by fusion-evaporation. The performances of the aforementioned ingredients of the upgrade (targets, 1+ source and charge breeder) have been and are still being optimized in the frame of different European projects (EMILIE, ENSAR and ENSAR2). The upgraded SPIRAL 1 facility will provide soon its first new beams for physics and further beam development are undertaken to prepare for the next AGATA campaign. The results obtained during the on-line commissioning period permit to evaluate intensities for new beams from the upgraded facility. © 2001 Elsevier Science. All rights reserved.