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The nature of the Verwey transition occurring at TV ≈ 125 K in magnetite (Fe3O4) has been an outstanding problem over many decades. A complex low temperature electronic order was recently discovered and associated structural fluctuations persisting above TV are widely reported, but the origin of the underlying correlations and hence of the Verwey transition remains unclear. Here we show that local structural fluctuations in magnetite emerge below the Curie transition at TC ≈ 850 K, through X-ray pair distribution function analysis. Around 80% of the low temperature correlations emerge in proportion to magnetization below TC. This confirms that fluctuations in Fe-Fe bonding arising from magnetic order are the primary electronic instability and hence the origin of the Verwey transition. Such hidden instabilities may be important to other spin-polarised conductors and orbitally degenerate materials., The Verwey transition in magnetite was reported 80 years ago but identifying the underlying mechanism has been difficult. Here the authors show that structural distortions associated with the Verwey transition emerge as local fluctuations at the Curie temperature, confirming their link with magnetic order. more...

The beam diffusing properties of stacked layers of diffuser material were evaluated experimentally and compared to a Gaussian random phase screen model. The model was found to give promising accuracy in combination with a Lorentzian auto-correlation model. The tail behaviour of the angular scattering distribution as a function of number of diffusing layers was particularly well described by the model, and in the case of an amorphous carbon diffuser, the model could describe the whole of the scattering distribution convincingly. (C) 2019 Optical Society of America under the terms of the OSA Open Access Publishing Agreement more...

The influence of nanosilica on the crystallization behavior, rheology and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites was investigated. It was found that the effect of nanofiller addition is dependent on the molar mass of the polymer matrix. For the higher molar mass matrix, a modest nucleation effect was observed, while in the lower molar mass matrices, this effect was absent. For the investigated range of filler contents, a modest increase in both modulus and ultimate tensile properties of the composites was observed. Lower molar mass matrices revealed voiding during deformation, which could be partly suppressed by the addition of nanofiller. The higher molar mass matrix showed no voiding in either the neat polymer or nanocomposite. more...

International audience; Zircon is the most widely used mineral in petrochronology and provides key information about magmatic and crustal differentiation history of plutonic rocks, transport paths of clastic material 'from source to sink' and significantly contributes in the reconstruction of enigmatic planetary-scale tectonic episodes since the Archaean. However, detailed textural analysis of this accessory mineral has always been hampered by two-dimensional (2D) analytical limitations. With the advancements in X-ray nanotomography technology, it is now possible to non-destructively, yet digitally, cut, visualize, compare and quantify internal textures within zircons, their growth and zoning patterns and chemical distribution of trace elements in three dimensions (3D). We present a novel multimodal approach of using a synchrotron radiation nanobeam to perform 3D nanopetrography of < 100 mu m zircons at similar to 100 nm resolution, demonstrating the capabilities of the technique by analysis of Paleoproterozoic zircons from the Central Finland Granitoid Complex. The integrated X-ray absorption, diffraction and fluorescence tomography revealed sector and oscillatory zoning patterns in 3D as well as differences in zoning pattern between trace elements, in addition to lattice parameters and inclusion composition within zircons. The multimodal synchrotron nanotomography elucidates the 3D nanopetrography and trace element composition of submillimeter-sized zircons in unprecedented detail. more...

A practical experimental procedure for transmission X-ray ghost imaging (XGI) using synchrotron light is presented. The authors demonstrate the method, discuss data acquisition and analysis, and measure the point-spread function of an XGI system. The generalization of the methods for future experiments is also discussed., An experimental procedure for transmission X-ray ghost imaging using synchrotron light is presented. Hard X-rays from an undulator were divided by a beamsplitter to produce two copies of a speckled incident beam. Both beams were simultaneously measured on an indirect pixellated detector and the intensity correlation between the two copies was used to retrieve the ghost image of samples placed in one of the two beams, without measuring the samples directly. Aiming at future practical uses of X-ray ghost imaging, the authors discuss details regarding data acquisition, image reconstruction strategies and measure the point-spread function of the ghost-imaging system. This approach may become relevant for applications of ghost imaging with X-ray sources such as undulators in storage rings, free-electron lasers and lower-coherence laboratory facilities. more...

Ti-alloys represent the principal structural materials in both aerospace development and metallic biomaterials. Key to optimizing their mechanical and functional behaviour is in-depth know-how of their phases and the complex interplay of diffusive vs. displacive phase transformations to permit the tailoring of intricate microstructures across a wide spectrum of configurations. Here, we report on structural changes and phase transformations of Ti–Nb alloys during heating by in situ synchrotron diffraction. These materials exhibit anisotropic thermal expansion yielding some of the largest linear expansion coefficients (+ 163.9×10−6 to −95.1×10−6 °C−1) ever reported. Moreover, we describe two pathways leading to the precipitation of the α-phase mediated by diffusion-based orthorhombic structures, α″lean and α″iso. Via coupling the lattice parameters to composition both phases evolve into α through rejection of Nb. These findings have the potential to promote new microstructural design approaches for Ti–Nb alloys and β-stabilized Ti-alloys in general., Nature Communications, 8 (1), ISSN:2041-1723 more...

Human dental pulp stem cells (hDPSCs) are mesenchymal stem cells that have been successfully used in human bone tissue engineering. To establish whether these cells can lead to a bone tissue ready to be grafted, we checked DPSCs for their osteogenic and angiogenic differentiation capabilities with the specific aim of obtaining a new tool for bone transplantation. Therefore, hDPSCs were specifically selected from the stromal-vascular dental pulp fraction, using appropriate markers, and cultured. Growth curves, expression of bone-related markers, calcification and angiogenesis as well as an in vivo transplantation assay were performed. We found that hDPSCs proliferate, differentiate into osteoblasts and express high levels of angiogenic genes, such as vascular endothelial growth factor and platelet-derived growth factor A. Human DPSCs, after 40 days of culture, give rise to a 3D structure resembling a woven fibrous bone. These woven bone (WB) samples were analysed using classic histology and synchrotron-based, X-ray phase-contrast microtomography and holotomography. WB showed histological and attractive physical qualities of bone with few areas of mineralization and neovessels. Such WB, when transplanted into rats, was remodelled into vascularized bone tissue. Taken together, our data lead to the assumption that WB samples, fabricated by DPSCs, constitute a noteworthy tool and do not need the use of scaffolds, and therefore they are ready for customized regeneration. Human dental pulp stem cells (hDPSCs) are mesenchymal stem cells that have been successfully used in human bone tissue engineering. To establish whether these cells can lead to a bone tissue ready to be grafted, we checked DPSCs for their osteogenic and angiogenic differentiation capabilities with the specific aim of obtaining a new tool for bone transplantation. Therefore, hDPSCs were specifically selected from the stromal-vascular dental pulp fraction, using appropriate markers, and cultured. Growth curves, expression of bone-related markers, calcification and angiogenesis as well as an in vivo transplantation assay were performed. We found that hDPSCs proliferate, differentiate into osteoblasts and express high levels of angiogenic genes, such as vascular endothelial growth factor and platelet-derived growth factor A. Human DPSCs, after 40 days of culture, give rise to a 3D structure resembling a woven fibrous bone. These woven bone (WB) samples were analysed using classic histology and synchrotron-based, X-ray phase-contrast microtomography and holotomography. WB showed histological and attractive physical qualities of bone with few areas of mineralization and neovessels. Such WB, when transplanted into rats, was remodelled into vascularized bone tissue. Taken together, our data lead to the assumption that WB samples, fabricated by DPSCs, constitute a noteworthy tool and do not need the use of scaffolds, and therefore they are ready for customized regeneration. more...

Intrauterine growth restriction (IUGR) is a fetal condition that affects up to 10% of all pregnancies and is associated with cardiovascular structural and functional remodelling that persists postnatally. Some studies have reported an increase in myocardial coronary blood flow in severe IUGR fetuses which has been directly associated to the dilatation of the coronary arteries. However, a direct measurement of the coronaries’ lumen diameter in IUGR has not been reported before. The aim of this paper is to perform, for the first time, a quantitative analysis of the effects of IUGR in cardiac geometry and coronary vessel size in a well-known rabbit model of IUGR using synchrotron-based X-ray Phase Contrast Tomography Imaging (X-PCI). Eight rabbit fetal hearts were imaged non-destructively with X-PCI. 3D reconstructions of the coronary arterial tree were obtained after semi-automatic image segmentation. Different morphometric features including vessel lumen diameter of the three main coronaries were automatically quantified. IUGR fetuses had more globular hearts and dilated coronary arteries as compared to controls. We have quantitatively shown that IUGR leads to structural coronary vascular tree remodelling and enlargement as an adaptation mechanism in response to an adverse environment of restricted oxygen and nutrients and increased perfusion pressure., PLoS ONE, 14 (6), ISSN:1932-6203 more...

The crystal structures of new layered manganese bismuth tellurides with the compositions Mn0.85(3)Bi4.10(2)Te7 and Mn0.73(4)Bi6.18(2)Te10 were determined by single-crystal X-ray diffraction, including the use of microfocused synchrotron radiation. These analyses reveal that the layered structures deviate from the idealized stoichiometry of the 12P-GeBi4Te7 (space group P3m1) and 51R-GeBi6Te10 (space group R3m) structure types they adopt. Modified compositions Mn1–xBi4+2x/3Te7 (x = 0.15 – 0.2) and Mn1–xBi6+2x/3Te10 (x = 0.19 – 0.26) assume cation vacancies and lead to homogenous bulk samples as confirmed by Rietveld refinements. Electron diffraction patterns exhibit no diffuse streaks that would indicate stacking disorder. The alternating quintuple-layer [M2Te3] and septuple-layer [M3Te4] slabs (M = mixed occupied by Bi and Mn) with 1:1 sequence (12P stacking) in Mn0.85Bi4.10Te7 and 2:1 sequence (51R stacking) in Mn0.81Bi6.13Te10 were also observed in HRTEM images. Temperature-dependent powder diffraction and differential scanning calorimetry show that the compounds are high temperature phases, which are metastable at ambient temperature. Magnetization measurements are in accordance with a MnII oxidation state and point at predominantly ferromagnetic coupling in both compounds. The thermoelectric figures of merit of n-type conducting Mn0.85Bi4.10Te7 and Mn0.81Bi6.13Te10 reach zT = 0.25 at 375 °C and zT = 0.28 at 325 °C, respectively. Although the compounds are metastable, compact ingots exhibit still up to 80% of the main phases after thermoelectric measurements up to 400 °C. more...

The operando methodology dictates not only that catalysts are analysed during reaction while activity and selectivity are monitored by analytical methods, but also that the cell in which the measurement is carried out performs as a catalytic reactor. A cell (Chiarello et al., Rev. Sci. Inst. 85 (2014) 074102) used to conduct spectroscopy and diffraction measurements under operando conditions was tested for CO oxidation on a 2 wt% Pt/Al2O3 catalyst and compared with measurements in a conventional quartz catalytic reactor to demonstrate its suitability to derive kinetic data. High energy X-ray diffraction data were collected during alternate CO and O2 pulses under differential conditions to demonstrate the extent of loss of order of the Pt particles upon exposure to the O2 pulse. The presence of a surface oxide species places the catalyst in a higher activity regime compared to the fully reduced one. more...

Methane oxidation over Pd–Pt/$ \mathrm{Al}_2\text{ O}_3 $ model catalysts calcined at three different conditions is investigated using operando diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry, and in situ X-ray absorption spectroscopy while cycling the feed gas stoichiometry between lean (net-oxidising) and rich (net-reducing) conditions. When calcined in air, alloy Pd–Pt nanoparticles are present only on catalysts subjected to elevated temperature ($ 800\,^{\circ }\mathrm{C} $) whereas calcination at lower temperature (500 $ ^{\circ }\mathrm{C} $) leads to segregated Pt and Pd nanoparticles on the support. Here, we show that the alloy Pd–Pt nanoparticles undergo reversible changes in surface structure and composition during transient methane oxidation exposing a PdO surface during lean conditions and a metallic Pd–Pt surface (Pd enriched) under rich conditions. Alloyed particles seem more active for methane oxidation than their monometallic counterparts and, furthermore, an increased activity for methane oxidation is clearly observed under lean conditions when PdO has developed on the surface, analogous to monometallic Pd catalysts. Upon introducing rich conditions, partial oxidation of methane dominates over total oxidation forming adsorbed carbonyls on the noble metal particles. The carbonyl spectra for the three samples show clear differences originating from different surfaces exposed by alloyed vs. non-alloyed particles. The kinetics of the noble metal oxidation and reduction processes as well as carbonyl formation during transient methane oxidation are discussed. more...

We present a phase reconstruction scheme for X-ray near-field holographic imaging based on a separability constraint for probe and object. In order to achieve this, we have devised an algorithm which requires only two measurements – with and without an object in the beam. This scheme is advantageous if the standard flat-field correction fails and a full ptychographic dataset can not be acquired, since either object or probe are dynamic. The scheme is validated by numerical simulations and by a proof-of-concept experiment using highly focused undulator radiation of the beamline ID16A of the European Synchrotron Radiation Facility (ESRF). more...

Understanding the complex crystallization behavior of isotactic polypropylene (iPP) in conditions comparable to those found in polymer processing, where the polymer melt experiences a combination of high shear rates and elevated pressures, is key for modeling and therefore predicting the final structure and properties of iPP products. Coupling a unique experimental setup, capable to apply wall shear rates similar to those experienced during processing and carefully control the pressure before and after flow is imposed, with in situ X-ray scattering and diffraction techniques (SAXS and WAXD) at fast acquisition rates (up to 30 Hz), a well-defined series of short-term flow experiments are carried out using 16 different combinations of wall shear rates (ranging from 110 to 440 s–1) and pressures (100–400 bar). A complete overview on the kinetics of structure development during and after flow is presented. Information about shish formation and growth of α-phase parents lamellae from the shish backbones is extracted from SAXS; the overall apparent crystallinity evolution, amounts of different phases (α, β, and γ), and morphologies developing in the shear layer (parent and daughter lamellae both in α and γ phase) are fully quantified from the analysis of WAXD data. Both flow rate and pressure were found to have a significant influence on the nucleation and the growth process of oriented and isotropic structures. Flow affects shish formation and the growth of α-parents; pressure acts on relaxation times, enhancing the effect of flow, and (mainly) on the growth rate of γ-phase. The remarkably high amount of γ-lamellae found in the oriented layer strongly indicates the nucleation of γ directly from the shish backbone. All the observations were conceptually in agreement with the flow-induced crystallization model framework developed in our group and represent a unique and valuable data set that will be used to further validate and implement our numerical modeling, filling the gap for quantitatively modeling crystallization during complicated processing operations like injection molding. more...

A La-Sr/CaO catalyst was studied operando during the oxidative coupling of methane (OCM) reaction using the X-ray diffraction computed tomography technique. Full-pattern Rietveld analysis was performed in order to track the evolving solid-state chemistry during the temperature ramp, OCM reaction, as well as after cooling to room temperature. We observed a uniform distribution of the catalyst main components: La2O3, CaO-SrO mixed oxide, and the high-temperature rhombohedral polymorph of SrCO3. These were stable initially in the reaction; however, doubling the gas hourly space velocity resulted in the decomposition of SrCO3 to SrO, which subsequently led to the formation of a second CaO-SrO mixed oxide. These two mixed CaO-SrO oxides differed in terms of the extent of Sr incorporation into their unit cell. By applying Vegard's law during the Rietveld refinement, it was possible to create maps showing the spatial variation of Sr occupancy in the mixed CaO-SrO oxides. The formation of the Sr-doped CaO species is expected to have an important role in this system through the enhancement of the lattice oxygen diffusion as well as increased catalyst basicity. more...

By means of high-energy synchrotron X-ray diffraction, the interplay between martensite and retained austenite phases in steel during the application of stress has been analyzed. Martensite properties were varied through controlled reheating heat treatments in a low carbon Quenched and Partitioned (Q&P) steel consisting of retained austenite and martensite. The reheating treatments significantly altered martensite strength while keeping the same fractions of retained austenite as the non-reheated Q&P microstructures, resulting in different degrees of stress partitioning and work hardening of the individual microconstituents. Results of this study show that the strength ratio between the different phases in the microstructure plays a crucial role in the onset and rate of mechanically induced decomposition of retained austenite. Consequently, the strength ratio between phases controls the yielding and work-hardening of the material. more...

Residual stresses originating from elasto-plastic deformation during mechanical processing can be analyzed post-process with various known methods. A new measurement method to measure and evaluate the strain and stress fields in situ under the contact point during a deep rolling process was developed to describe the dependence of the residual stresses from the internal material load. Using synchrotron radiation at European Synchrotron Radiation Facility (ESRF) (ID11), diffraction measurements were performed in transmission geometry during dynamical loading with different process parameters. The strain and stress fields were analyzed with high spatial resolution in an 8 mm &times, 4 mm area around the contact point during the process using a 13-mm tungsten carbide roller on samples of AISI 4140H steel. Fast data acquisition allowed the reconstruction of full two-dimensional (2D) strain and stress maps. These could be used to determine the response from the initial material state in front of the roller to the mechanically loaded region with plastic deformation up to the processed material with the resulting residual stresses. This comprehensive analysis was then used to link the internal material load with the resulting residual stresses in the final material state. more...

The determination of residual stresses (RS) through X-Ray Diffraction (XRD) necessitates the knowledge of the X-Ray Elastic Constants (XEC) S1 and 1/2 S2 for the specific phase in presence. In the case of Ti-6Al-4V additive manufacturing (AM) elaboration method such as Powder Bed Laser Beam Melting (PB-LBM) results in a microstructure fully constituted α’ martensitic phase. The properties of this α’ martensite are largely unknown. The purpose of the present paper is to determine the XEC of the α’ martensitic phase. This is performed using an original methodology involving 2D X-Ray detection. The results shows significant differences with XEC values available for the α phase from Titanium. more...

Supplementary information accompanies this paper at https://doi.org/10.1038/s41598-018-31849-w.; International audience; Human vocal folds possess outstanding abilities to endure large, reversible deformations and to vibrate up to more than thousand cycles per second. This unique performance mainly results from their complex specific 3D and multiscale structure, which is very difficult to investigate experimentally and still presents challenges using either confocal microscopy, MRI or X-ray microtomography in absorption mode. To circumvent these difficulties, we used high-resolution synchrotron X-ray microtomography with phase retrieval and report the first ex vivo 3D images of human vocal-fold tissues at multiple scales. Various relevant descriptors of structure were extracted from the images: geometry of vocal folds at rest or in a stretched phonatory-like position, shape and size of their layered fibrous architectures, orientation, shape and size of the muscle fibres as well as the set of collagen and elastin fibre bundles constituting these layers. The developed methodology opens a promising insight into voice biomechanics, which will allow further assessment of the micromechanics of the vocal folds and their vibratory properties. This will then provide valuable guidelines for the design of new mimetic biomaterials for the next generation of artificial larynges. more...

International audience; Scholars have debated the taxonomic identity of isolated primate teeth from the Asian Pleis-tocene for over a century, which is complicated by morphological and metric convergence between orangutan (Pongo) and hominin (Homo) molariform teeth. Like Homo erectus, Pongo once showed considerable dental variation and a wide distribution throughout mainland and insular Asia. In order to clarify the utility of isolated dental remains to document the presence of hominins during Asian prehistory, we examined enamel thickness, enamel-den-tine junction shape, and crown development in 33 molars from G. H. R. von Koenigswald's Chinese Apothecary collection (11 Sinanthropus officinalis [= Homo erectus], 21 "Heman-thropus peii," and 1 "Hemanthropus peii" or Pongo) and 7 molars from Sangiran dome (either Homo erectus or Pongo). All fossil teeth were imaged with non-destructive conventional and/or synchrotron micro-computed tomography. These were compared to H. erectus teeth from Zhoukoudian, Sangiran and Trinil, and a large comparative sample of fossil Pongo, recent Pongo, and recent human teeth. We find that Homo and Pongo molars overlap substantially in relative enamel thickness; molar enamel-dentine junction shape is more distinctive, with Pongo showing relatively shorter dentine horns and wider crowns than Homo. Long-period line periodicity values are significantly greater in Pongo than in H. erec-tus, leading to longer crown formation times in the former. Most of the sample originally assigned to S. officinalis and H. erectus shows greater affinity to Pongo than to the hominin comparative sample. Moreover, enamel thickness, enamel-dentine junction shape, and a long-period line periodicity value in the "Hemanthropus peii" sample are indistinguishable from fossil Pongo. These results underscore the need for additional recovery and study of associated dentitions prior to erecting new taxa from isolated teeth. more...

International audience; In this paper, ultrasound measurements of 1:1 scale three-dimensional (3D) printed trabecular bone phantoms are reported. The micro-structure of a trabecular horse bone sample was obtained via synchrotron x-ray microtomography, converted to a 3D binary data set, and successfully 3D-printed at scale 1:1. Ultrasound through-transmission experiments were also performed through a highly anisotropic version of this structure, obtained by elongating the digitized structure prior to 3D printing. As in real anisotropic trabecular bone, both the fast and slow waves were observed. This illustrates the potential of stereolithography and the relevance of such bone phantoms for the study of ultrasound propagation in bone. more...

The feasibility for multi-speckle XPCS measurements in the ultra-low-angle range is demonstrated. The performance of the setup is illustrated by means of colloidal dynamics., Multi-speckle X-ray photon correlation spectroscopy (XPCS) measurements in the ultra-small-angle range are performed using a long pinhole collimation instrument in combination with two-dimensional photon-counting and high-sensitivity imaging detectors. The feasibility of the presented setup to measure dynamics on different time and length scales pertinent to colloidal systems is shown. This setup offers new research opportunities, such as for example in the investigation of non-equilibrium dynamics in optically opaque, complex systems over length scales from tens of nanometres to several micrometres. In addition, due to the short duration of the X-ray exposure involved in the ultra-small-angle range, possible radiation-induced effects are alleviated. Furthermore, the performance of two different detectors, a photon-counting Pilatus 300K and an integrating FReLoN CCD, are compared, and their applicability for accurate XPCS measurements is demonstrated. more...

X-ray nanodiffraction is used to evaluate axial and tangential residual stress distributions in a W thin film deposited on the scalloped inner wall of a through-silicon via. The results reveal oscillatory stress distributions which correlate well with the scallop wavelength and morphology., Synchrotron X-ray nanodiffraction is used to analyse residual stress distributions in a 200 nm-thick W film deposited on the scalloped inner wall of a through-silicon via. The diffraction data are evaluated using a novel dedicated methodology which allows the quantification of axial and tangential stress components under the condition that radial stresses are negligible. The results reveal oscillatory axial stresses in the range of ∼445–885 MPa, with a distribution that correlates well with the scallop wavelength and morphology, as well as nearly constant tangential stresses of ∼800 MPa. The discrepancy with larger stress values obtained from a finite-element model, as well as from a blanket W film, is attributed to the morphology and microstructural nature of the W film in the via. more...

This Perspective is part of the Up and Coming series. Abstract: Over the past few decades material scientists have developed a wide variety of approaches to deliberately introduce chemical and structural inhomogeneities into nanoparticles achieving for example intentional doping concentration gradients and multicomponent structures. This perspective presents a sense of how modern hard X ray spectroscopic methods far from merely providing new tools are extending the way we study and understand such complex nanoparticles. Particularly the possibility to select with high resolution the incident and emission hard X ray energies offers unprecedented site selectivity and rapid data acquisition helps to uncover the complex chemical world behind the state of the art synthetic methods like hot injection Brust Schiffrin supercritical flow and nonaqueous synthesis. Therefore today the in situ spectroscopic studies provide a new view into the genesis of heterogeneity in colloidal nanoparticles. more...

The theoretical description and experimental implementation of a speckle-tracking-based instrument which permits the characterisation of X-ray pulse wavefronts., An instrument allowing the quantitative analysis of X-ray pulsed wavefronts is presented and its processing method explained. The system relies on the X-ray speckle tracking principle to accurately measure the phase gradient of the X-ray beam from which beam optical aberrations can be deduced. The key component of this instrument, a semi-transparent scintillator emitting visible light while transmitting X-rays, allows simultaneous recording of two speckle images at two different propagation distances from the X-ray source. The speckle tracking procedure for a reference-less metrology mode is described with a detailed account on the advanced processing schemes used. A method to characterize and compensate for the imaging detector distortion, whose principle is also based on speckle, is included. The presented instrument is expected to find interest at synchrotrons and at the new X-ray free-electron laser sources under development worldwide where successful exploitation of beams relies on the availability of an accurate wavefront metrology. more...

International audience; Many organisms use amorphous calcium carbonate (ACC) and control its stability by various additives and water; however, the underlying mechanisms are yet unclear. Here, the effect of water and inorganic additives commonly found in biology on the dynamics of the structure of ACC during crystallization and on the energetics of this process is studied. Total X-ray scattering and pair distribution function analysis show that the short- and mediumrange order of all studied ACC samples are similar; however, the use of in situ methodologies allow the observation of small structural modifications that are otherwise easily overlooked. Isothermal calorimetric coupled with microgravimetric measurements show that the presence of Mg2+ and of PO43− in ACC retards the crystallization whereas increased water content accelerates the transformation. The enthalpy of ACC with respect to calcite appears, however, independent of the additive concentration but decreases with water content. Surprisingly, the enthalpic contribution of water is compensated for by an equal and opposite entropic term leading to a net independence of ACCthermodynamic stability on its hydration level. Together, these results point toward a kinetic stabilization effect of inorganic additives and water, and may contribute to the understanding of the biological control of mineral stability. more...

International audience; The effect of the support material and chemical state of Rh in Rh/A(2)O(3) and Rh/SiO2 model catalysts during CO2 hydrogenation were studied by a combined array of in situ characterisation techniques including diffuse reflectance infrared Fourier transform spectroscopy, energy-dispersive X-ray absorption spectroscopy and high-energy X-ray diffraction at 250-350 degrees C and atmospheric pressure. CO2 methanation proceeds via intermediate formation of adsorbed CO species on metallic Rh, likely followed by their hydrogenation to methane. The linearly-bonded CO species is suggested to be a more active precursor in the hydrogenation compared to the bridge-bonded species, which seems to be related to particle size effects: for larger particles mainly the formation of inactive bridge-bonded CO species takes place. Further, analysis of the chemical state of Rh under the reaction conditions reveal a minor formation of RhOx from dissociation of CO2, which is a consequence of the increased activity observed over the Rh/Al2O3 catalyst. more...

International audience; Synchrotron-generated microplanar beams (microbeams) provide the most stereo-selective irradiation modality known today. This novel irradiation modality has been shown to control seizures originating from eloquent cortex causing no neurological deficit in experimental animals. To test the hypothesis that application of microbeams in the hippocampus, the most common source of refractory seizures, is safe and does not induce severe side effects, we used microbeams to induce transections to the hippocampus of healthy rats. An array of parallel microbeams carrying an incident dose of 600 Gy was delivered to the rat hippocampus. Immunohistochemistry of phosphorylated gamma-H2AX showed cell death along the microbeam irradiation paths in rats 48 hours after irradiation. No evident behavioral or neurological deficits were observed during the 3-month period of observation. MR imaging showed no signs of radio-induced edema or radionecrosis 3 months after irradiation. Histological analysis showed a very well preserved hippocampal cytoarchitecture and confirmed the presence of clear-cut microscopic transections across the hippocampus. These data support the use of synchrotron-generated microbeams as a novel tool to slice the hippocampus of living rats in a minimally invasive way, providing (i) a novel experimental model to study hippocampal function and (ii) a new treatment tool for patients affected by refractory epilepsy induced by mesial temporal sclerosis. more...

The high-temperature creep behavior of a rafted [001] oriented AM1 Ni-based single crystal superalloy was investigated during in situ creep tests on synchrotrons. Experiments were performed at constant temperatures under variable applied stress in order to study the response (plastic strain, load transfer) to stress jumps. Using two different diffraction techniques in transmission (Laue) geometry, it was possible to measure the average lattice parameters of both the &gamma, matrix and the &gamma, &prime, rafts in the [100] direction at intervals shorter than 300 s. The absolute precision with both diffraction techniques of the constrained transverse mismatch (in the rafts&rsquo, plane) is about 10&minus, 5. After stress jumps, special attention is given to the evolution of plastic strain within the &gamma, channels. The relaxation of the Von Mises stress at leveled applied stress shows evidence of dislocation multiplication within the &gamma, channels. From the analysis, we showed an interaction between plastic stress and dislocation density of the &gamma, phase. more...

Recent years have seen the development of new iron-centered N-heterocyclic carbene (NHC) complexes for solar energy applications. Compared to typical ligand systems, the NHC ligands provide Fe complexes with longer-lived metal-to-ligand charge transfer (MLCT) states. This increased lifetime is ascribed to strong ligand field splitting provided by the NHC ligands that raises the energy levels of the metal centered (MC) states and therefore reduces the deactivation efficiency of MLCT states. Among currently known NHC systems, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazol-1-ylidene)pyridine) is a unique complex as it exhibits a short-lived MC state with a lifetime on the scale of a few hundreds of picoseconds. Hence, this complex allows for a detailed investigation, using 100 ps X-ray pulses from a synchrotron, of strong ligand field effects on the intermediate MC state in an NHC complex. Here, we use time-resolved wide angle X-ray scattering (TRWAXS) aided by density functional theory (DFT) to investigate the molecular structure, energetics and lifetime of the high-energy MC state in the Fe-NHC complex [Fe(btbip)2]2+ after excitation to the MLCT manifold. We identify it as a 260 ps metal-centered quintet (5MC) state, and we refine the molecular structure of the excited-state complex verifying the DFT results. Using information about the hydrodynamic state of the solvent, we also determine, for the first time, the energy of the 5MC state as 0.75 + 0.15 eV. Our results demonstrate that due to the increased ligand field strength caused by NHC ligands, upon transition from the ground state to the 5MC state, the metal to ligand bonds extend by unusually large values: by 0.29 angstrom in the axial and 0.21 angstrom in the equatorial direction. These results imply that the transition in the photochemical properties from typical Fe complexes to novel NHC compounds is manifested not only in the destabilization of the MC states, but also in structural distortion of these states. more...

We describe here a partial skull with associated mandible of a large felid from Monte Argentario, Italy (Early Pleistocene; ~1.5 million years). Propagation x-ray phase-contrast synchrotron microtomography of the specimen, still partially embedded in the rock matrix, allows ascribing it reliably to Acinonyx pardinensis, one of the most intriguing extinct carnivorans of the Old World Plio-Pleistocene. The analysis of images and 3D models obtained through synchrotron microtomography – here applied for the first time on a Plio-Pleistocene carnivoran – reveals a mosaic of cheetah-like and Panthera-like features, with the latter justifying previous attributions of the fossil to the extinct Eurasian jaguar Panthera gombaszoegensis. Similarly, we reassign to A. pardinensis some other Italian materials previously referred to P. gombaszoegensis (sites of Pietrafitta and Ellera di Corciano). The recognition of Panthera-like characters in A. pardinensis leads to reconsidering the ecological role of this species, whose hunting strategy was likely to be different from those of the living cheetah. Furthermore, we hypothesise that the high intraspecific variation in body size in A. pardinensis can be the result of sexual dimorphism, as observed today in all large-sized felids. more...

International audience; Gorgonopsia is one of the major clades of non-mammalian synapsids, and includes an array of large-bodied carnivores that were the top terrestrial predators of the late Permian. Most research on the clade has focused on these largest members; small-bodied gorgonopsians are relatively little-studied. Here, we redescribe a small gorgonopsian skull (MB.R.999) from the late Permian (Tropidostoma Assemblage Zone) of South Africa on the basis of neutron and synchrotron CT reconstructions, which yield new data on internal cranial morphology in Gorgonopsia. Because of the largely undistorted nature of MB.R.999, we were also able to reconstruct unossified areas such as the brain endocast and the otic labyrinth. MB.R.999 can be referred to the taxon Cynariops robustus based on its general skull proportions, postcanine tooth count, preparietal morphology, and vomerine morphology. We refer additional small gorgonopsian specimens from the Victoria West area to Cynariops robustus, and consider Cynarioides grimbeeki and Cynarioides laticeps to be synonymous with C. robustus. Inclusion of Cynariops in a phylogenetic analysis of Gorgonopsia recovers it within a large clade of African taxa, more closely related to Lycaenops and rubidgeines than Eriphostoma or Gorgonops. more...

Both a cured cement paste and a paste undergoing in situ hydration have been characterized using state-of-the-art synchrotron diffraction tomography. The mineralogy, macroporosity and carbonation phenomena of the samples have been determined., To understand the main properties of cement, a ubiquitous material, a sound description of its chemistry and mineralogy, including its reactivity in aggressive environments and its mechanical properties, is vital. In particular, the porosity distribution and associated sample carbonation, both of which affect cement’s properties and durability, should be quantified accurately, and their kinetics and mechanisms of formation known both in detail and in situ. However, traditional methods of cement mineralogy analysis (e.g. chemical mapping) involve sample preparation (e.g. slicing) that can be destructive and/or expose cement to the atmosphere, leading to preparation artefacts (e.g. dehydration). In addition, the kinetics of mineralogical development during hydration, and associated porosity development, cannot be examined. To circumvent these issues, X-ray diffraction computed tomography (XRD-CT) has been used. This allowed the mineralogy of ternary blended cement composed of clinker, fly ash and blast furnace slag to be deciphered. Consistent with previous results obtained for both powdered samples and dilute systems, it was possible, using a consolidated cement paste (with a water-to-solid ratio akin to that used in civil engineering), to determine that the mineralogy consists of alite (only detected in the in situ hydration experiment), calcite, calcium silicate hydrates (C-S-H), ettringite, mullite, portlandite, and an amorphous fraction of unreacted slag and fly ash. Mineralogical evolution during the first hydration steps indicated fast ferrite reactivity. Insights were also gained into how the cement porosity evolves over time and into associated spatially and time-resolved carbonation mechanisms. It was observed that macroporosity developed in less than 30 h of hydration, with pore sizes reaching about 100–150 µm in width. Carbonation was not observed for this time scale, but was found to affect the first 100 µm of cement located around macropores in a sample cured for six months. Regarding this carbonation, the only mineral detected was calcite. more...

While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided. more...

A method is proposed which enables the retrieval of the thickness or of the projected electron density of a sample from a single input image acquired with an edge illumination phase-contrast imaging setup. The method assumes the case of a quasi-homogeneous sample, i.e. a sample with a constant ratio between the real and imaginary parts of its complex refractive index. Compared with current methods based on combining two edge illumination images acquired in different configurations of the setup, this new approach presents advantages in terms of simplicity of acquisition procedure and shorter data collection time, which are very important especially for applications such as computed tomography and dynamical imaging. Furthermore, the fact that phase information is directly extracted, instead of its derivative, can enable a simpler image interpretation and be beneficial for subsequent processing such as segmentation. The method is first theoretically derived and its conditions of applicability defined. Quantitative accuracy in the case of homogeneous objects as well as enhanced image quality for the imaging of complex biological samples are demonstrated through experiments at two synchrotron radiation facilities. The large range of applicability, the robustness against noise and the need for only one input image suggest a high potential for investigations in various research subjects. more...

Heterostructures of germanium antimony tellurides with skutterudite-type precipitates are promising thermoelectric materials due to low thermal conductivity and multiple ways of tuning their electronic transport properties. Materials with the nominal composition [CoSb2(GeTe)_(0.5)]_x(GeTe)_(10.5)Sb_2Te_3 (x = 0–2) contain nano- to microscale precipitates of skutterudite-type phases which are homogeneously distributed. Powder X-ray diffraction reveals that phase transitions of the germanium antimony telluride matrix depend on its GeTe content. These are typical for this class of materials; however, the phase transition temperatures are influenced by heterostructuring in a beneficial way, yielding a larger existence range of the intrinsically nanostructured pseudocubic structure of the matrix. Using microfocused synchrotron radiation in combination with crystallite pre-selection by means of electron microscopy, single crystals of the matrix as well as of the precipitates were examined. They show nano-domain twinning of the telluride matrix and a pronounced structure distortion in the precipitates caused by GeTe substitution. Thermoelectric figures of merit of 1.4 ± 0.3 at 450 °C are observed. In certain temperature ranges, heterostructuring involves an improvement of up to 30% compared to the homogeneous material. more...

The alpha-(Per)(2)[M(mnt)(2)] compounds with M = Pt and Au are isostructural two-chain solids that in addition to partially oxidized conducting perylene chains also contain anionic chains that can be either paramagnetic in the case of M = Pt or diamagnetic for M = Au. The electrical transport and magnetic properties of the solid solutions (Per)(2)[Pt-x-Au(1-x)(mnt)(2)] were investigated. The incorporation of paramagnetic [Pt(mnt)(2)] impurities in the diamagnetic chains, and the effect of breaking the paramagnetic chains with diamagnetic centers for the low and high Pt range of concentrations were respectively probed. In the low Pt concentration range, there is a fast decrease of the metal-to-insulator transition from 12.4 K in the pure Au compound to 9.7 K for x = 0.1 comparable to the 8.1 K in the pure Pt compound. In the range x = 0.5-0.95, only beta-phase crystals could be obtained. The spin-Peierls transition of the pure Pt compound, simultaneous with metal-to-insulator (Peierls) transition is still present for 2% of diamagnetic impurities (x = 0.98) with transition temperature barely affected. Single crystal X-ray diffraction data obtained a high-quality structural refinement of the alpha- phase of the Au and Pt compounds. The beta-phase structure was found to be composed of ordered layers with segregated donors and anion stacks, which alternate with disordered layers. The semiconducting properties of the beta-phase are due to the disorder localization effects. info:eu-repo/semantics/publishedVersion more...

Bragg diffraction imaging enables the quality of synthetic single-crystal diamond substrates and their overgrown, mostly doped, diamond layers to be characterized. This is very important for improving diamond-based devices produced for X-ray optics and power electronics applications. The usual first step for this characterization is white-beam X-ray diffraction topography, which is a simple and fast method to identify the extended defects (dislocations, growth sectors, boundaries, stacking faults, overall curvatureetc.) within the crystal. This allows easy and quick comparison of the crystal quality of diamond plates available from various commercial suppliers. When needed, rocking curve imaging (RCI) is also employed, which is the quantitative counterpart of monochromatic Bragg diffraction imaging. RCI enables the local determination of both the effective misorientation, which results from lattice parameter variation and the local lattice tilt, and the local Bragg position. Maps derived from these parameters are used to measure the magnitude of the distortions associated with polishing damage and the depth of this damage within the volume of the crystal. For overgrown layers, these maps also reveal the distortion induced by the incorporation of impurities such as boron, or the lattice parameter variations associated with the presence of growth-incorporated nitrogen. These techniques are described, and their capabilities for studying the quality of diamond substrates and overgrown layers, and the surface damage caused by mechanical polishing, are illustrated by examples. more...

Human IgG4 antibody shows therapeutically useful properties compared with the IgG1, IgG2, and IgG3 subclasses. Thus IgG4 does not activate complement and shows conformational variability. These properties are attributable to its hinge region, which is the shortest of the four IgG subclasses. Using high throughput scattering methods, we studied the solution structure of wild-type IgG4(Ser222) and a hinge mutant IgG4(Pro222) in different buffers and temperatures where the proline substitution suppresses the formation of half-antibody. Analytical ultracentrifugation showed that both IgG4 forms were principally monomeric with sedimentation coefficients s20,w0 of 6.6–6.8 S. A monomer-dimer equilibrium was observed in heavy water buffer at low temperature. Scattering showed that the x-ray radius of gyration Rg was unchanged with concentration in 50–250 mm NaCl buffers, whereas the neutron Rg values showed a concentration-dependent increase as the temperature decreased in heavy water buffers. The distance distribution curves (P(r)) revealed two peaks, M1 and M2, that shifted below 2 mg/ml to indicate concentration-dependent IgG4 structures in addition to IgG4 dimer formation at high concentration in heavy water. Constrained x-ray and neutron scattering modeling revealed asymmetric solution structures for IgG4(Ser222) with extended hinge structures. The IgG4(Pro222) structure was similar. Both IgG4 structures showed that their Fab regions were positioned close enough to the Fc region to restrict C1q binding. Our new molecular models for IgG4 explain its inability to activate complement and clarify aspects of its stability and function for therapeutic applications. more...

We have studied the effect of pressure and temperature on the location of the pivotal surface in a lipid inverse bicontinuous gyroid cubic phase (Q(G)(II)), described by the area at the pivotal surface (An), the volume between the pivotal surface and the bilayer midplane (Vn), and the molecular volume of the lipid (V). Small angle X-ray scattering (SAXS) was used to measure the swelling behaviour of the lipid, monolinolein, as a function of pressure and temperature, and the data were fitted to two different geometric models: the parallel interface model (PIM), and the constant mean curvature model (CMCM). The results show that an increase in temperature leads to a shift in the location of the pivotal surface towards the bilayer midplane, whilst an increase in pressure causes the pivotal surface to move towards the interfacial region. In addition, we describe the relevance of An, Vn and V for modeling the energetics of curved mesophases with specific reference to the mean curvature at the pivotal surface and discuss the significance of this parameter for modelling the energetics of curved mesophases. more...

An in situ study with dispersive EXAFS (Extended X-Ray Absorption Spectroscopy) at the Ir-LIIIedge is performed to characterize Electrodeposited Iridium Oxide Films (EIROF) under chronoamperometric conditions. The technique monitors the local chemical environment and electronic structure of iridium during the oxidation of Ir(III) to Ir(IV) with a time resolution of milliseconds. The study is performed in both acidic and basic media. The Fourier transforms of the time-resolved EXAFS signals clearly show that the short-range structure of Ir is similar to that of rutile-type IrO2and is maintained during the reaction, thus accounting for the flexibility of the structure of the electrode material in accommodating different oxidation states. From a more general point of view, the work demonstrates the capabilities of in situ experiments based on state-of-the-art dispersive EXAFS in clarifying the mechanistic aspects of electrochemical processes. more...

International audience; Phase imaging coupled to micro-tomography acquisition has emerged as a powerful tool to investigate specimens in a non-destructive manner. While the intensity data can be acquired and recorded, the phase information of the signal has to be “retrieved” from the data modulus only. Phase retrieval is an ill-posed non-linear problem and regularization techniques including a priori knowledge are necessary to obtain stable solutions. Several linear phase recovery methods have been proposed and it is expected that some limitations resulting from the linearization of the direct problem will be overcome by taking into account the non-linearity of the phase problem. To achieve this goal, we propose and evaluate a non-linear algorithm for in-line phase micro-tomography based on an iterative Landweber method with an analytic calculation of the Fréchet derivative of the phase-intensity relationship and of its adjoint. The algorithm was applied in the projection space using as initialization the linear mixed solution. The efficacy of the regularization scheme was evaluated on simulated objects with a slowly and a strongly varying phase. Experimental data were also acquired at ESRF using a propagation-based X-ray imaging technique for the given pixel size 0.68 μm. Two regularization scheme were considered: first the initialization was obtained without any prior on the ratio of the real and imaginary parts of the complex refractive index and secondly a constant a priori value was assumed on r δ β . The tomographic central slices of the refractive index decrement were compared and numerical evaluation was performed. The non-linear method globally decreases the reconstruction errors compared to the linear algorithm and is achieving better reconstruction results if no prior is introduced in the initialization solution. For in-line phase micro-tomography, this non-linear approach is a new and interesting method in biomedical studies where the exact value of the a priori ratio is not known. more...

Full thickness human skin models (FTMs) contain an epidermal and a dermal equivalent. The latter is composed of a collagen dermal matrix which harbours fibroblasts. Current epidermal barrier properties of FTMs do not fully resemble that of native human skin (NHS), which makes these human skin models less suitable for barrier related studies. To further enhance the resemblance of NHS for epidermal morphogenesis and barrier formation, we modulated the collagen dermal matrix with the biocompatible polymer chitosan. Herein, we report that these collagen-chitosan FTMs (CC-FTMs) possess a well-organized epidermis and maintain both the early and late differentiation programs as in FTMs. Distinctively, the epidermal cell activation is reduced in CC-FTMs to levels observed in NHS. Dermal-epidermal interactions are functional in both FTM types, based on the formation of the basement membrane. Evaluation of the barrier structure by the organization of the extracellular lipid matrix of the stratum corneum revealed an elongated repeat distance of the long periodicity phase. The ceramide composition exhibited a higher resemblance of the NHS, based on the carbon chain-length distribution and subclass profile. The inside-out barrier functionality indicated by the transepidermal water loss is significantly improved in the CC-FTMs. The expression of epidermal barrier lipid processing enzymes is marginally affected, although more restricted to a single granular layer. The novel CC-FTM resembles the NHS more closely, which makes them a promising tool for epidermal barrier related studies. more...

Studies of brain cytoarchitecture in mammals are routinely performed by serial sectioning of the specimen and staining of the sections. The procedure is labor-intensive and the 3D architecture can only be determined after aligning individual 2D sections, leading to a reconstructed volume with non-isotropic resolution. Propagation-based x-ray phase-contrast tomography offers a unique potential for high-resolution 3D imaging of intact biological specimen due to the high penetration depth and potential resolution. We here show that even compact laboratory CT at an optimized liquid-metal jet microfocus source combined with suitable phase-retrieval algorithms and a novel tissue preparation can provide cellular and subcellular resolution in millimeter sized samples of mouse brain. We removed water and lipids from entire mouse brains and measured the remaining dry tissue matrix in air, lowering absorption but increasing phase contrast. We present single-cell resolution images of mouse brain cytoarchitecture and show that axons can be revealed in myelinated fiber bundles. In contrast to optical 3D techniques our approach does neither require staining of cells nor tissue clearing, procedures that are increasingly difficult to apply with increasing sample and brain sizes. The approach thus opens a novel route for high-resolution high-throughput studies of brain architecture in mammals. more...

International audience; Synapsida, the clade including therapsids and thus also mammals, is one of the two major branches of amniotes. Organismal design, with modularity as a concept, offers insights into the evolution of therapsids, a group that experienced profound anatomical transformations throughout the past 270 Ma, eventually leading to the evolution of the mammalian bauplan. However, the anatomy of some therapsid groups remains obscure. Gorgonopsian braincase anatomy is poorly known and many anatomical aspects of the brain, cranial nerves, vasculature, and osseous labyrinth, remain unclear. We analyzed two gorgonopsian specimens, GPIT/RE/7124 and GPIT/RE/7119, using propagation phase contrast synchrotron micro- computed tomography. The lack of fusion between many basicranial and occipital bones in GPIT/RE/7124, which is an immature specimen, allowed us to reconstruct its anatomy and ontogenetic sequence, in comparison with the mature GPIT/RE/7119, in great detail. We explored the braincase and rendered various skull cavities. Notably, we found that there is a separate ossification between what was previously referred to as the ``parasphenoid'' and the basioccipital. We reinterpreted this element as a posterior ossification of the basisphenoid: the basipostsphenoid. Moreover, we show that the previously called ``parasphenoid'' is in fact the co-ossification of the dermal parasphenoid and the endochondral basipresphenoid. In line with previous descriptions, the anatomy of the osseous labyrinth is rendered in detail, revealing a unique discoid morphology of the horizontal semicircular canal, rather than toroidal, probably due to architectural constraints of the ossification of the opisthotic and supraoccipital. In addition, the orientation of the horizontal semicircular canal suggests that gorgonopsians had an anteriorly tilted alert head posture. The morphology of the brain endocast is in accordance with the more reptilian endocast shape of other non-mammaliaform neotherapsids more...

The effect of ceria doping by oxide surface modification and controlled metal surface modification (CSM) on the structure-function properties of Rh/γ-Al2O3 catalysts in the process of CO oxidation were studied by a combined array of Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)/Energy Dispersive X-ray Absorption Fine Structure/Mass Spectrometry techniques applied simultaneously under time-resolved, in situ conditions in the temperature range of 298–573 K. The addition of each promoter element by CSM exhibits multiple effects on the catalysts structure. The DRIFTS/XAS studies indicate that CeOx facilitate the protection of Rh particles against extensive oxidation in atmospheres of air, O2 and CO, without reducing the coverage of oxidisable adsorbed CO. more...

Oesophageal tissue engineering is a therapeutic alternative when oesophageal replacement is required. Decellularised scaffolds are ideal as they are derived from tissue-specific extracellular matrix and are non-immunogenic. However, appropriate preservation may significantly affect scaffold behaviour. Here we aim to prove that an effective method for short- and long-term preservation can be applied to tissue engineered products allowing their translation to clinical application. Rabbit oesophagi were decellularised using the detergent-enzymatic treatment (DET), a combination of deionised water, sodium deoxycholate and DNase-I. Samples were stored in phosphate-buffered saline solution at 4°C (4°C) or slow cooled in medium with 10% Me2SO at -1°C/min followed by storage in liquid nitrogen (SCM). Structural and functional analyses were performed prior to and after 2 and 4 weeks and 3 and 6 months of storage under each condition. Efficient decellularisation was achieved after 2 cycles of DET as determined with histology and DNA quantification, with preservation of the ECM. Only the SCM method, commonly used for cell storage, maintained the architecture and biomechanical properties of the scaffold up to 6 months. On the contrary, 4°C method was effective for short-term storage but led to a progressive distortion and degradation of the tissue architecture at the following time points. Efficient storage allows a timely use of decellularised oesophagi, essential for clinical translation. Here we describe that slow cooling with cryoprotectant solution in liquid nitrogen vapour leads to reliable long-term storage of decellularised oesophageal scaffolds for tissue engineering purposes. more...

International audience; There are two types of dermal skeletons in jawed vertebrates: placoderms and osteichthyans carry large bony plates (macromery), whereas chondrichthyans and acanthodians are covered by small scales (micromery). Fin spines are one of the last large dermal structures found on micromeric taxa and offer a potential source of histology and morphology that can be compared to those found on macromeric groups. Dermal fin spines offer a variety of morphology but aspects of their growth modes and homology are unclear. Here, we provide detailed descriptions of the microstructure and growth of a dorsal ridge spine from the acanthothoracid placoderm, Romundina stellina, using virtual three-dimensional paleohistological datasets. From these data we identify several layers of dentine ornamentation covering the lateral surfaces of the spine and reconstructed their growth pattern. We show that this spine likely grew posteriorly and proximally from a narrow portion of bone located along the leading edge of the spine. The spine is similarly constructed to the scales with a few exceptions, including the absence of polarized fibers distributed throughout the bone and the presence of a thin layer of perichondral bone. The composition of the spine (semidentine odontodes, dermal bone, perichondral bone) is identical to that of the Romundina dermal plates. These results illustrate the similarities and differences between the dermal tissues in Romundina and indicate that the spine grew differently from the dentinous fin spines from extant and fossil chondrichthyans. The morphology and histology of Romundina is most similar to the fin spine of the probable stem osteichthyan Lophosteus, with a well-developed inner cellular bony base and star-shaped odontodes on the surface. Results from these studies will undoubtedly have impact on our understanding of fossil fin spine histology and evolution, contributing to the on-going revision of early gnathostome phylogeny. more...

International audience; A novel experimental setup is presented to reveal damage mechanisms in bast fibers. 3D imaging at submicronic scale based on X-ray micro-tomography is combined with in-situ tensile experiments of both elementary fibers and bundles. The results reveal that the relevant scale that drives failure of hemp lignocellulosic fibers is submicronic. In-situ tensile experiments assisted by X-ray micro-tomography shows complex damage mechanisms involving the constitutive sub-layer structure, fiber extraction defects like kink bands, and the tubular porosity of the natural fiber. more...

This paper presents a multifunctional polymer surface that provides superhydrophobicity and self–cleaning functions together with an enhancement in mechanical and electrical performance. These functionalities are produced by nanoimprinting high aspect ratio pillar arrays on polymeric matrix incorporating functional reinforcing elements. Two distinct matrix-filler systems are investigated specifically, Carbon Nanotube reinforced Polystyrene (CNT-PS) and Reduced Graphene Oxide reinforced Polyvinylidene Difluoride (RGO-PVDF). Mechanical characterization of the topographies by quantitative nanoindentation and nanoscratch tests are performed to evidence a considerable increase in stiffness, Young’s modulus and critical failure load with respect to the pristine polymers. The improvement on the mechanical properties is rationalized in terms of effective dispersion and penetration of the fillers into the imprinted structures as determined by confocal Raman and SEM studies. In addition, an increase in the degree of crystallization for the PVDF-RGO imprinted nanocomposite possibly accounts for the larger enhancement observed. Improvement of the mechanical ruggedness of functional textured surfaces with appropriate fillers will enable the implementation of multifunctional nanotextured materials in real applications. more...