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Of the 7–8 silk fibers making up an orb-web only the hierarchical structural organization of semicrystalline radial fibers -composed of major ampullate silk- has been studied in detail, given its fascinating mechanical features. While major ampullate silk's nanofibrillar morphology is well established, knowhow on mesoscale (> 50–100 nm) assembly and its contribution to mechanical performance is limited. Much less is known on the hierarchical structural organization of other, generally less crystalline fibers contributing to an orb-webs' function. Here we show by scanning X-ray micro&nanodiffraction that two fully amorphous, fine silk fibers from the center of an orb-web have different mesoscale features. One of the fibers has a fibrillar composite structure resembling stiff egg case silk. The other fiber has a skin–core structure based on a nanofibrillar ribbon wound around a disordered core. A fraction of nanofibrils appears to have assembled into mesoscale fibrils. This fiber becomes readily attached to the coat of major ampullate silk fibers. We observe that a detached fiber has ripped out the glycoprotein skin-layer containing polyglycine II nanocrystallites. The anchoring of the fiber in the coat suggests that it could serve for strengthening the tension and cohesion of major ampullate silk fibers. [ABSTRACT FROM AUTHOR]

Examines the use of undulator X-ray sources in the development of microfocusing optics for wide-angle and small-angle scattering (WAXS/SAXS). Mechanics of a pinhole collimating system; Information on the resolution of X-ray beams; Feasibility of performing SAXS/WAXS experiments in a single detector setting.

Focuses on the small-angle scattering and fiber diffraction analysis of the morphology of single native cellulose fibers. Mechanisms involved in azimuthal broadenings; Physical effects of the misalignment of crystalline cellulose microfibrils; Factors contributing to disordered cellulose fiber set-up.

Shear localisation in thin bands is an important process involved in the plastic deformation of materials subject to stress. This process is often sensitive to the sample microstructure (amorphous/crystalline). Here we show using the scanning µ-SAXS technique, how these different microstructures influence the plastic deformations in a drying colloidal film. In crystalline samples, the presence of an ordering transition at the compaction front was directly identified through the development of a six-fold symmetry in the scattering pattern in 20 wt% samples. It is shown that plastic deformations in individual groups of particles during the compaction process can be tracked and measured in real time. Higher concentration suspensions were found to result in amorphous structures. The transition between crystalline and amorphous microstructures with initial particle concentration was also found to correlate with the appearance of shear bands. Through 2D spatial mapping of the local film structure, the presence of shear bands in the films was directly related to the microscale spatial variations in strain magnitude and compression direction. Our measurements also showed that shear bands lead to a reduction in the local particle volume fraction ~1-2%, indicating significant dilatancy. [ABSTRACT FROM AUTHOR]

Langmuir–Blodgett protein nanofilms can serve as templates for nucleation and growth of protein crystals. This functionality can be enhanced by thermal annealing. While surface ordering of the multilayered nanofilms and an improvement of the correlation between the layers during thermal annealing have been revealed by atomic force microscopy and grazing-incidence small-angle x-ray scattering, information on the structure developing in the bulk of nanofilms is lacking. In this paper, we report on scanning x-ray nanodiffraction experiments of penicillin-G-acylase multilayers deposited on Si3N4 membranes and annealed at 150 °C. While the annealed multilayer has remained mostly featureless, we observe locally globular aggregates and filamentous spherulites based on nanofibrillar subunits with cross-β amyloidic motifs. [ABSTRACT FROM AUTHOR]

While it is known that the nature and the arrangement of defects in complex oxides have an impact on the material functionalities, little is known about control of superconductivity by oxygen interstitial organization in cuprates. Here we report direct compelling evidence for the control of Tc by manipulation of the superconducting granular networks of nanoscale puddles, made of ordered oxygen stripes, in a single crystal of YBa2Cu3O6.5 + y with average formal hole doping p close to 1/8. Upon thermal treatments we were able to switch from a first network of oxygen defect striped puddles with OVIII modulation (qOVIII(a*) = (h + 3/8, k, 0) and qOVIII(a*) = (h + 5/8, k, 0)) to a second network characterized by OXVI modulation (qOXVI(a*) = (h + 7/16, k, 0) and qox-VI(a*) = (h + 9/16, k, 0)) and finally to a third network with puddles of OV periodicity (qOV(a*) = (4/10, 1, 0) and qOV(a*) = (6/10, 1, 0)). We map the microscopic spatial evolution of the out of plane OVIII, OXVI and OV puddle nano-size distribution via scanning micro-diffraction measurements. In particular, we calculated the number of oxygen chains (n) and the charge density (hole concentration p) inside each puddle, analyzing areas of 160 × 80 μm2, and recording 12 800 diffraction patterns to reconstruct each spatial map. The high spatial inhomogeneity shown by all the reconstructed spatial maps reflects the intrinsic granular structure that characterizes cuprates and iron chalcogenides, disclosing the presence of several complex networks of coexisting superconducting domains with different lattice modulations, charge densities and gaps as in the proposed multi-gap scenario called superstripes. [ABSTRACT FROM AUTHOR]

Regenerated cellulose fibers have been considered as potential precursor fibers for carbon fibers because of their balanced cost and performance. Increased attention has been paid to blending lignin with the regenerated cellulose to generate precursor fibers which render good mechanical properties and higher carbon yield. The mechanical properties of carbon fibers have been found closely correlated to the structure of precursor fibers. However, the effects of lignin blending on molecular- and morphological structure of the precursor are still unclear. This study aims at clarifying the structural information of lignin–cellulose precursor fibers from molecular level to mesoscale by scanning X-ray microdiffraction. We present the existence of a skin–core morphology for all the precursor fibers. Increase of lignin content in precursor fiber could reduce the portion of skin and cause obvious disorder of the meso- and molecular structure. By correlating structural variations with lignin blending, 30% lignin blending has been found as a potential balance point to obtain precursor fibers maintaining structural order together with high yield rate. [Display omitted] [ABSTRACT FROM AUTHOR]

Quantitative X‐ray diffraction approaches require careful correction for sample transmission. Though this is a routine task at state‐of‐the‐art small‐angle X‐ray scattering (SAXS), wide‐angle X‐ray scattering (WAXS) or diffraction beamlines at synchrotron facilities, the transmission signal cannot be recorded concurrently with SAXS/WAXS when using the small, sub‐millimetre beamstops at many X‐ray nanoprobes during SAXS/WAXS experiments due to the divergence‐limited size of the beamstop and the generally tight geometry. This is detrimental to the data quality and often the only solution is to re‐scan the sample with a PIN photodiode as a detector to obtain transmission values. In this manuscript, we present a simple yet effective solution to this problem in the form of a small beamstop with an inlaid metal target for optimal fluorescence yield. This fluorescence can be detected with a high‐sensitivity avalanche photodiode and provides a linear counter to determine the sample transmission. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bone mineralization in osteosarcomas differs from healthy bone. • Decreased carbonate content suggests high turnover. • Crystal lattice distortions are compatible with B-type carbonate substitution. • Two osteosarcomas of different subtypes show different structure and stoichiometry. • Structure and stoichiometry are compared to those of bone metastases from literature. Osteosarcoma (OS) is the most common malignant primary bone tumor in humans and occurs in various subtypes. Tumor formation happens through malignant osteoblasts producing immature bone. In the present paper we studied two different subtypes of osteosarcoma, from one individual with conventional OS with massive sclerosis and one individual with parosteal OS, based on a multimodal approach including small angle x-ray scattering (SAXS), wide angle x-ray diffraction (WAXS), backscattered electron imaging (BEI) and Raman spectroscopy. It was found that both tumors showed reduced mineral particle sizes and degree of orientation of the collagen-mineral composite in the affected areas, alongside with a decreased crystallinity. Distinct differences between the tumor material from the two individuals were found in the degree of mineralization. Further differences were observed in the carbonate to phosphate ratio, which is related to the degree of carbonate substitution in bone mineral and indicative of the turnover rate. The contraction of the c-axis of the bone mineral crystals proved to be a further, very sensitive parameter, potentially indicative of malignancy. [ABSTRACT FROM AUTHOR]

At the ESRF, two complementary XRPD-based techniques are increasingly used by the cultural heritage community: high angular resolution X-ray powder diffraction (HR-XRPD) and micro X-ray powder diffraction (µXRPD) mapping. For the past 20 years, the community of heritage scientists has frequently exploited the synchrotron radiation-based techniques offered at the European Synchrotron Radiation Facility (ESRF), Grenoble, France [[1]]. Prior tomography experiments at the ESRF were restricted by the beam and sample stage sizes to a maximum sample diameter of 18 cm (e.g., [[11]]), making impossible the imaging of many large and scientifically impactful natural and cultural heritage samples. [Extracted from the article]

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the "block allocation group" (BAG) mode. Here, we present the recently implemented "historical materials BAG": a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines—ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses—with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood. [ABSTRACT FROM AUTHOR]

Biofilms are multicellular microbial communities that encase themselves in an extracellular matrix (ECM) of secreted biopolymers and attach to surfaces and interfaces. Bacterial biofilms are detrimental in hospital and industrial settings, but they can be beneficial, for example, in agricultural as well as in food technology contexts. An essential property of biofilms that grants them with increased survival relative to planktonic cells is phenotypic heterogeneity, the division of the biofilm population into functionally distinct subgroups of cells. Phenotypic heterogeneity in biofilms can be traced to the cellular level; however, the molecular structures and elemental distribution across whole biofilms, as well as possible linkages between them, remain unexplored. Mapping X-ray diffraction across intact biofilms in time and space, we revealed the dominant structural features in Bacillus subtilis biofilms, stemming from matrix components, spores, and water. By simultaneously following the X-ray fluorescence signal of biofilms and isolated matrix components, we discovered that the ECM preferentially binds calcium ions over other metal ions, specifically, zinc, manganese, and iron. These ions, remaining free to flow below macroscopic wrinkles that act as water channels, eventually accumulate and may possibly lead to sporulation. The possible link between ECM properties, regulation of metal ion distribution, and sporulation across whole, intact biofilms unravels the importance of molecular-level heterogeneity in shaping biofilm physiology and development. [ABSTRACT FROM AUTHOR]

Lead–calcium phosphates are unusual compounds sometimes found in different kinds of cultural heritage objects. Structural and physicochemical properties of this family of materials, which fall into the hydroxypyromorphite–hydroxyapatite solid solution, or (Pb x Ca1−x)5(PO4)3OH, have received considerable attention during the last few decades for promising applications in different fields of environmental and material sciences, but their diagnostic implications in the cultural heritage context have been poorly explored. This paper aims to provide a clearer understanding of the relationship between compositional and structural properties of the peculiar series of (Pb x Ca1−x)5(PO4)3OH solid solutions and to determine key markers for their proper non-destructive and non-invasive identification in cultural heritage samples and objects. For this purpose, a systematic study of powders and paint mock-ups made up of commercial and in-house synthesized (Pb x Ca1−x)5(PO4)3OH compounds with a different Pb2+/Ca2+ ratio was carried out via a multi-technique approach based on scanning electron microscopy, synchrotron radiation-based X-ray techniques, i.e., X-ray powder diffraction and X-ray absorption near edge structure spectroscopy at the Ca K- and P K-edges, and vibrational spectroscopy methods, i.e., micro-Raman and Fourier transform infrared spectroscopy. The spectral modifications observed in the hydroxypyromorphite–hydroxyapatite solid solution series are discussed, by assessing the advantages and disadvantages of the proposed techniques and by providing reference data and optimized approaches for future non-destructive and non-invasive applications to study cultural heritage objects and samples. [ABSTRACT FROM AUTHOR]

Living matter is a quasi-stationary out-of-equilibrium system; in this physical condition, structural fluctuations at nano- and meso-scales are needed to understand the physics behind its biological functionality. Myelin has a simple ultrastructure whose fluctuations show correlated disorder in its functional out-of-equilibrium state. However, there is no information on the relationship between this correlated disorder and the dynamics of the intrinsically disordered Myelin Basic Protein (MBP) which is expected to influence the membrane structure and overall functionality. In this work, we have investigated the role of this protein structural dynamics in the myelin ultrastructure fluctuations in various conditions, by using synchrotron Scanning micro X Ray Diffraction and Small Angle X ray Scattering. We have induced the crossover from out-of-equilibrium functional state to in-equilibrium degeneration changing the pH to values far from physiological condition. The observed compression of the cytosolic layer thickness probes that the intrinsic large MBP fluctuations preserve the cytosol structure also in the degraded state. Thus, the transition of myelin ultrastructure from correlated to uncorrelated disordered state, is principally affected by the deformation of the membrane and extracellular domain. Unlabelled Image • Myelin structure in pH degraded state from Scanning micro X ray diffraction. • Myelin basic protein (MBP) conformation from small angle X ray scattering. • Myelin correlated disorder become uncorrelated disorder towards pH denaturation. • MBP remains the principal active protein after pH denaturation. • MBP help to preserve myelin structure both in functional and in pH degraded state. [ABSTRACT FROM AUTHOR]

Sliding friction causes significant structural transformations in the subsurface layers of interacting materials. These changes are associated with complicated mechanochemical processes which include but not limited to plastic flow, refinement of structure, increase of dislocation density, oxidation, delamination and formation of wear debris. In this study we attempted to observe some of these processes using synchrotron X-ray diffraction using operando and ex situ approaches. For this reason a special friction tester was used, which allows probing the surface layer of the sample using X-ray microbeam. The research was carried out at Beamline ID13 of the European Synchrotron Radiation Facility. The as-quenched medium-carbon steel AISI-5135 was used in experiments. The effect of friction on X-ray line broadening, texturing and formation of iron oxides was analysed and discussed. [ABSTRACT FROM AUTHOR]

The clean and reproducible conditions provided by microfluidic devices are ideal sample environments for in situ analyses of chemical and biochemical reactions and assembly processes. However, the small size of microchannels makes investigating the crystallization of poorly soluble materials on-chip challenging due to crystal nucleation and growth that result in channel fouling and blockage. Here, we demonstrate a reusable insert-based microfluidic platform for serial X-ray diffraction analysis and examine scale formation in response to continuous and segmented flow configurations across a range of temperatures. Under continuous flow, scale formation on the reactor walls begins almost immediately on mixing of the crystallizing species, which over time results in occlusion of the channel. Depletion of ions at the start of the channel results in reduced crystallization towards the end of the channel. Conversely, segmented flow can control crystallization, so it occurs entirely within the droplet. Consequently, the spatial location within the channel represents a temporal point in the crystallization process. Whilst each method can provide useful crystallographic information, time-resolved information is lost when reactor fouling occurs and changes the solution conditions with time. The flow within a single device can be manipulated to give a broad range of information addressing surface interaction or solution crystallization. [ABSTRACT FROM AUTHOR]

X‐ray imaging is a complementary method to electron and fluorescence microscopy for studying biological cells. In particular, scanning small‐angle X‐ray scattering provides overview images of whole cells in real space as well as local, high‐resolution reciprocal space information, rendering it suitable to investigate subcellular nanostructures in unsliced cells. One persisting challenge in cell studies is achieving high throughput in reasonable times. To this end, a fast scanning mode is used to image hundreds of cells in a single scan. A way of dealing with the vast amount of data thus collected is suggested, including a segmentation procedure and three complementary kinds of analysis, i.e. characterization of the cell population as a whole, of single cells and of different parts of the same cell. The results show that short exposure times, which enable faster scans and reduce radiation damage, still yield information in agreement with longer exposure times. [ABSTRACT FROM AUTHOR]

The article explores the novel structural features of the mapping the three-dimensional orientation of nanocrystals and nanostructures in human bone. It discusses the reconstruction of the three-dimensional orientation in human lamellar bone of both the nanoscale features and the biomineral crystal lattice from small-angle x-ray scattering and wide-angle x-ray scattering, respectively.

Gadolinium-based contrast agents (GBCAs) are frequently used in patients undergoing magnetic resonance imaging. In GBCAs gadolinium (Gd) is present in a bound chelated form. Gadolinium is a rare-earth element, which is normally not present in human body. Though the blood elimination half-life of contrast agents is about 90 minutes, recent studies demonstrated that some tissues retain gadolinium, which might further pose a health threat due to toxic effects of free gadolinium. It is known that the bone tissue can serve as a gadolinium depot, but so far only bulk measurements were performed. Here we present a summary of experiments in which for the first time we mapped gadolinium in bone biopsy from a male patient with idiopathic osteoporosis (without indication of renal impairment), who received MRI 8 months prior to biopsy. In our studies performed by means of synchrotron radiation induced micro- and submicro-X-ray fluorescence spectroscopy (SR-XRF), gadolinium was detected in human cortical bone tissue. The distribution of gadolinium displays a specific accumulation pattern. Correlation of elemental maps obtained at ANKA synchrotron with qBEI images (quantitative backscattered electron imaging) allowed assignment of Gd structures to the histological bone structures. Follow-up beamtimes at ESRF and Diamond Light Source using submicro-SR-XRF allowed resolving thin Gd structures in cortical bone, as well as correlating them with calcium and zinc. [ABSTRACT FROM AUTHOR]

Radiation damage limits the accuracy of macromolecular structures in X-ray crystallography. Cryogenic (cryo-) cooling reduces the global radiation damage rate and, therefore, became the method of choice over the past decades. The recent advent of serial crystallography, which spreads the absorbed energy over many crystals, thereby reducing damage, has rendered room temperature (RT) data collection more practical and also extendable to microcrystals, both enabling and requiring the study of specific and global radiation damage at RT. Here, we performed sequential serial raster-scanning crystallography using a microfocused synchrotron beam that allowed for the collection of two series of 40 and 90 full datasets at 2- and 1.9-Å resolution at a dose rate of 40.3 MGy/s on hen egg white lysozyme (HEWL) crystals at RT and cryotemperature, respectively. The diffraction intensity halved its initial value at average doses (D1/2) of 0.57 and 15.3 MGy at RT and 100 K, respectively. Specific radiation damage at RT was observed at disulfide bonds but not at acidic residues, increasing and then apparently reversing, a peculiar behavior that can be modeled by accounting for differential diffraction intensity decay due to the nonuniform illumination by the X-ray beam. Specific damage to disulfide bonds is evident early on at RT and proceeds at a fivefold higher rate than global damage. The decay modeling suggests it is advisable not to exceed a dose of 0.38 MGy per dataset in static and time-resolved synchrotron crystallography experiments at RT. This rough yardstick might change for proteins other than HEWL and at resolutions other than 2 Å. [ABSTRACT FROM AUTHOR]

This work showcases a method to map the full deformation tensor in a single micro‐sized crystal. It is shown that measuring the position of two Bragg reflections in reciprocal space is sufficient to obtain the full deformation tensor, if the condition of incompressibility of the material is imposed. This method is used to reveal the surface tension induced deformation at the edges of an as‐grown single‐crystal VO2 microwire. All components of the deformation tensor of the microwire were measured down to an absolute value of 10−4 in an 8 × 14 µm projected area of the wire. With a beam‐defined spatial resolution of 150 × 150 nm, the measurement time was merely 2.5 h. [ABSTRACT FROM AUTHOR]

Cellulose in solution can be assembled into textile fibers by wet-spinning (Viscose etc.) or dry-jet wet spinning (Lyocell, Ioncell etc.), which leads to significant differences in the mechanical properties of fibers. We use scanning X-ray microdiffraction (SXM) to reveal regenerated fibers having a "skin-core" morphology. The "core" region comprises microfibrils (MFs) with ~100 nm in diameter. The cellulose forms elementary fibrils having a ribbon-like cross sectional shape of about 6 × 2 nm, which are packed into MFs. Our SXM studies demonstrate that MFs within Ioncell fibers are composed of elementary fibrils with homogeneous morphologies. Furthermore, the stacking of cellulose molecular sheets within elementary fibrils of Viscose fibers is preferentially along the 010 direction, while those of Ioncell fibers preferably stack in the 1–10 direction. The better structural regularities and distinct morphologies of elementary fibrils give Ioncell fibers enhanced mechanical properties and a wet strength far superior to those of Viscose fibers. [Display omitted] [ABSTRACT FROM AUTHOR]

The manufacturing steps and first tests of a refractive lens made of polycrystalline diamond are described. A fabrication process based on electron‐beam lithography and deep reactive ion etching is introduced. Experimental tests on beamline ID13 at the ESRF have been performed. A spot size of 360 nm (FWHM) at an energy E = 24.3 keV is observed. [ABSTRACT FROM AUTHOR]

Abstract Thin diamond films deposited by chemical vapour deposition (CVD) usually feature cross-sectional gradients of microstructure, residual stress and mechanical properties, which decisively influence their functional properties. This work introduces a novel correlative cross-sectional nano-analytics approach , which is applied to a multi-layered CVD diamond film grown using microwave plasma-enhanced CVD and consisting of a ∼8 μm thick nanocrystalline (NCD) base and a ∼14.5 μm thick polycrystalline (PCD) top diamond sublayers. Complementary cross-sectional 30 nm beam synchrotron X-ray diffraction, depth-resolved micro-cantilever and hardness testing and electron microscopy analyses reveal correlations between microstructure, residual stress and mechanical properties. The NCD sublayer exhibits a 1.5 μm thick isotropic nucleation region with the highest stresses of ∼1.3 GPa and defect-rich nanocrystallites. With increasing sublayer thickness, a 110 fibre texture evolves gradually, accompanied by an increase in crystallite size and a decrease in stress. At the NCD/PCD sublayer interface, texture, stresses and crystallite size change abruptly and the PCD sublayer exhibits the presence of Zone T competitive grain growth microstructure. NCD and PCD sublayers differ in fracture stresses of ∼14 and ∼31 GPa, respectively, as well as in elastic moduli and hardness, which are correlated with their particular microstructures. In summary, the introduced nano-analytics approach provides complex correlations between microstructure, stresses, functional properties and deposition conditions. Graphical abstract Image 10773 [ABSTRACT FROM AUTHOR]

In contrast to synthetic materials, materials produced by organisms are formed in ambient conditions and with a limited selection of elements. Nevertheless, living organisms reveal elegant strategies for achieving specific functions, ranging from skeletal support to mastication, from sensors and defensive tools to optical function. Using state-of-the-art characterization techniques, we present a biostrategy for strengthening and toughening the otherwise brittle calcite optical lenses found in the brittlestar Ophiocoma wendtii. This intriguing process uses coherent nanoprecipitates to induce compressive stresses on the host matrix, functionally resembling the Guinier-Preston zones known in classical metallurgy. We believe that these calcitic nanoparticles, being rich in magnesium, segregate during or just after transformation from amorphous to crystalline phase, similarly to segregation behavior from a supersaturated quenched alloy. [ABSTRACT FROM AUTHOR]

Dragline silk of Trichonephila spiders has attracted attention in various applications. One of the most fascinating uses of dragline silk is in nerve regeneration as a luminal filling for nerve guidance conduits. In fact, conduits filled with spider silk can measure up to autologous nerve transplantation, but the reasons behind the success of silk fibers are not yet understood. In this study dragline fibers of Trichonephila edulis were sterilized with ethanol, UV radiation, and autoclaving and the resulting material properties were characterized with regard to the silk's suitability for nerve regeneration. Rat Schwann cells (rSCs) were seeded on these silks in vitro and their migration and proliferation were investigated as an indication for the fiber's ability to support the growth of nerves. It was found that rSCs migrate faster on ethanol treated fibers. To elucidate the reasons behind this behavior, the fiber's morphology, surface chemistry, secondary protein structure, crystallinity, and mechanical properties were studied. The results demonstrate that the synergy of dragline silk's stiffness and its composition has a crucial effect on the migration of rSCs. These findings pave the way towards understanding the response of SCs to silk fibers as well as the targeted production of synthetic alternatives for regenerative medicine applications. [ABSTRACT FROM AUTHOR]

Along the line of the recent research topic aimed at understanding the in vivo activity of mineral fibres and their mechanisms of toxicity, this work describes the morpho-chemical characteristics of the mineral fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal/intrapleural injection of UICC chrysotile, UICC crocidolite and erionite-Na from Nevada (USA). The fibres are studied with in situ synchrotron powder diffraction and high resolution transmission electron microscopy to improve our understanding of the mechanisms of toxicity of these mineral fibres. In contact with the tissues of the rats, chrysotile fibres are prone to dissolve, with leaching of Mg and production of a silica rich relict. On the other hand, crocidolite and erionite-Na fibres are stable even for very long contact times within the tissues of the rats, showing just a thin dissolution amorphous halo. These findings support the model of a lower biopersistence of chrysotile with respect to crocidolite and erionite-Na but the formation of a silica-rich fibrous residue after the pseudo-amorphization of chrysotile may justify a higher cytotoxic potential and intense inflammatory activity of chrysotile in the short term in contact with the lung tissues. [ABSTRACT FROM AUTHOR]

Though hard and superhard ceramic nanocrystalline thin films exhibit extraordinary strength, they typically suffer from brittleness. The lack of plasticity and associated toughness in these materials is due to brittle fracture along grain boundaries of a low cohesive energy, which is favored over dislocation emission. The catastrophic intergranular fracture of ceramic films is undesirable in many applications and limits their exploitation potential despite of other exceptional physical properties. We demonstrate here that it is possible to increase fracture toughness of ceramic nanostructured materials of more than 150% by a dedicated grain boundary orientation design with respect to the direction of the expected crack path without loss of hardness. The concept was applied to nanocrystalline monolithic TiN thin films which were mechanically tested as notched and unnotched microcantilever specimens inside a scanning electron microscope. The films with a columnar chevron-like grain morphology exhibit multiple crack deflections at the kink planes of the repeatedly tilted grains resulting in energy dissipation at the crack tip and in an increase of fracture surface area. The results document that the number of predefined cross-sectional crack turns as well as the film density play decisive roles in the measured overall material fracture resistance. We suggest that by a dedicated design of grain boundary orientations, it is possible to synthetize novel types of hard and tough nanomaterials. [ABSTRACT FROM AUTHOR]

An approach to enhance the performance of protective hard coatings for cutting applications is to modify the coating architecture by combining two inherently different materials in a multilayer. Besides the choice of the materials, the thickness of the individual layers strongly influences the coating microstructure and consequently also its properties. Within this work, a graded ZrN/Ti 0.33 Al 0.67 N multilayer coating with constant Ti 0.33 Al 0.67 N and stepwise increasing ZrN layer thickness was investigated in detail by a combinatorial approach of cross-sectional X-ray nanodiffraction, electron backscatter diffraction and transmission electron microscopy. The primary aim was to obtain a profound understanding of the microstructure of the coating as well as of the residual stress state. (Semi-)coherent grain growth was observed independently of the ZrN layer thickness. Changes in the multilayer architecture were found to affect not only the grain size, but also the residual stress state of the coating. While the grain size increased with increasing ZrN layer thickness, the residual stress decreased. This work contributes to a deeper understanding of the influence of the multilayer architecture on the microstructure and stress state of heteroepitactic multilayer coatings. • Graded ZrN/Ti 0.33 Al 0.67 N multilayer coating deposited by cathodic arc evaporation • Constant Ti 0.33 Al 0.67 N and stepwise increasing ZrN layer thickness • Semi-coherent growth through layer interfaces • Grain size increases with increasing ZrN layer thickness. • Residual stress highest at low layer thickness, due to dominating coherency strain [ABSTRACT FROM AUTHOR]

As spun silkworm ( Bombyx mori ) silk fibers were compared in terms of their tensile behavior and microstructure with fibers subjected to different degumming treatments. Fibers were initially retrieved by forced silking directly from the worms and, either characterized in the as spun condition, or subjected to one of the following treatments: immersion in water, conventional degumming or degumming under longitudinally constrained conditions. Microstructure was assessed by X-ray diffraction and Raman spectroscopy. In addition, polyacrylamide gel electrophoresis was used to determine the influence of degumming on silk at a molecular level. Our study not only shows that degumming represents a major contribution to the accepted idea of silkworm silk as a highly variable material, but also provides new insights in the relationship between microstructure and tensile behavior in these fibers. In particular, it is shown that the arrangement of the hydrogen bond network in fibers subjected to different treatments plays a critical role in determining the mechanical behavior of silkworm silk. [ABSTRACT FROM AUTHOR]

A deeper comprehension of the biomineralization (BM) process is at the basis of tissue engineering and regenerative medicine developments. Several in-vivo and in-vitro studies were dedicated to this purpose via the application of 2D and 3D diagnostic techniques. Here, we develop a new methodology, based on different complementary experimental techniques (X-ray phase contrast tomography, micro-X-ray diffraction and micro-X-ray fluorescence scanning technique) coupled to new analytical tools. A qualitative and quantitative structural investigation, from the atomic to the micrometric length scale, is obtained for engineered bone tissues. The high spatial resolution achieved by X-ray scanning techniques allows us to monitor the bone formation at the first-formed mineral deposit at the organic–mineral interface within a porous scaffold. This work aims at providing a full comprehension of the morphology and functionality of the biomineralization process, which is of key importance for developing new drugs for preventing and healing bone diseases and for the development of bio-inspired materials. [ABSTRACT FROM AUTHOR]

Summary Eosinophils are white blood cells that function in innate immunity and participate in the pathogenesis of various inflammatory and neoplastic disorders. Their secretory granules contain four cytotoxic proteins, including the eosinophil major basic protein (MBP-1). How MBP-1 toxicity is controlled within the eosinophil itself and activated upon extracellular release is unknown. Here we show how intragranular MBP-1 nanocrystals restrain toxicity, enabling its safe storage, and characterize them with an X-ray-free electron laser. Following eosinophil activation, MBP-1 toxicity is triggered by granule acidification, followed by extracellular aggregation, which mediates the damage to pathogens and host cells. Larger non-toxic amyloid plaques are also present in tissues of eosinophilic patients in a feedback mechanism that likely limits tissue damage under pathological conditions of MBP-1 oversecretion. Our results suggest that MBP-1 aggregation is important for innate immunity and immunopathology mediated by eosinophils and clarify how its polymorphic self-association pathways regulate toxicity intra- and extracellularly. [ABSTRACT FROM AUTHOR]

CVD hard coatings deposited on cemented carbide substrates typically exhibit tensile residual stresses, which are mainly due to differences in the thermal expansion coefficients of coating and substrate material. However, CVD TiB 2 coatings have been reported to show considerable compressive residual stresses, with lacking information about their origin. Within this work, TiB 2 coatings were deposited with and without TiN base layers on cemented carbide substrates using thermally activated CVD. The coating composition was examined using glow discharge optical emission spectroscopy yielding a slight sub-stoichiometry of the nanocrystalline TiB 2 layers. Slices of the coating were prepared and synchrotron X-ray nanodiffraction experiments were performed in transmission geometry. Thus, gradients of stresses and texture could be determined as a function of the coating thickness. The TiN base layer showed tensile stresses, while the compressive stresses in the TiB 2 layer even further increased with increasing layer thickness. No pronounced orientation could be determined for the early growth stage of the TiB 2 layers, but with increasing thickness, a distinct (101) fiber texture develops. Pole figure measurements revealed no pronounced texture for the TiN base layer and corroborated the (101) texture for the TiB 2 top layer. Using the sin 2 ψ method, compressive stresses of ~ 2.9 GPa could be determined for the TiB 2 layers, which significantly relaxed after annealing at 1000 °C. Nanoindentation experiments revealed a hardness of ~ 44 GPa. In conclusion, the nanocrystalline nature of the coatings seems to be the dominating origin of the compressive stresses of CVD TiB 2 coatings. [ABSTRACT FROM AUTHOR]

Microfluidics combined with X-ray scattering techniques allows probing conformational changes or assembly processes of biological materials. Our aim was to develop a highly X-ray transparent microfluidic cell for detecting small variations of X-ray scattering involved in such processes. We describe the fabrication of a polyimide microfluidic device based on a simple, reliable and inexpensive lamination process. The implemented microstructured features result in windows with optimized X-ray transmission. The microfluidic device was characterized by X-ray microbeam scattering at the ID13 beamline of the European Synchrotron Radiation Facility. [ABSTRACT FROM AUTHOR]

Abstract: A new series of isostructural MOF-type carboxylates called MIL-116 (M2(OH)2[C12O12H2]·2H2O), was synthesized from the combination of mellitic acid and trivalent p cations M = Al3+, Ga3+ or In3+. Their structures were analyzed either by single-crystal microdiffraction using the synchrotron radiation beamline (ID13 station at ESRF, Grenoble) or solved from powder X-ray diffraction. The 3D hybrid framework is built up from the connection of infinite straight chains of metal-centered octahedra sharing trans corners linked to each other through the mellitate ligands. Here the ligand acts as octadentate linker with four of the carboxylic groups involved in the M–O–C bondings. The two other carboxylate arms remain non-bonded under their protonated form. This represents a rare case of the occurrence of both non-bonding and bonding organic functionalities in a MOF-type solid. Within the tunnels are located water species that interact with the non-coordinated –COOH groups pointing towards the channel. [Copyright &y& Elsevier]

Despite intensive research a physical explanation of high Tc superconductors remains elusive. One reason for this is that these materials have generally a very complex structure making useless theoretical models for a homogeneous system. Little is known on the control of the critical temperature by the space disposition of defects because of lack of suitable experimental probes. X-ray diffraction and neutron scattering experiments used to investigate y oxygen dopants in YBa2Cu3O6+y lack of spatial resolution. Here we report the spatial imaging of dopants distribution inhomogeneity in YBa2Cu3O6.67 using scanning nano X-ray diffraction. By changing the X-ray beam size from 1 micron to 300 nm of diameter, the lattice inhomogeneity increases. The ordered oxygen puddles size distribution vary between 6-8 nm using 1 3 1 mm2 beam, while it is between 5-12 nm with a fat tail using the 300 × 300 nm2 beam. The increased inhomogeneity at the nanoscale points toward a network of superconducting puddles made of ordered oxygen interstitials. [ABSTRACT FROM AUTHOR]

Oxygen chain fragments are known to appear at the insulator-to-superconductor transition in YBa2Cu3O6+y. However, the self-organization and the size distribution of oxygen chain fragments are not known. Here,- we seek to fill this gap, using scanning micro-x-ray diffraction, which is an imaging method based on advances in focusing a synchrotron radiation beam. This approach allows us to probe both real-space and k-space of high-quality YBa2Cu3O6.33 single crystals with Tc = 7 K. We report compelling evidence for nanoscale striped puddles, with Ortho-II structure, made of chain fragments in the basal Cu(1) plane with local oxygen concentration y ⩾ 0.5. The size of the Ortho-II puddles spans a range between 2 and 9 nm. The real-space imaging of Ortho-II puddles granular network shows that superconductivity, at a low hole-doping regime, occurs in a network of nanoscale oxygen ordered patches, interspersed with oxygen depleted regions. The manipulation by thermal treatments of the striped Ortho-II puddles has been investigated focusing on the spontaneous symmetry breaking near the order-to-disorder phase transition at T0 = 350 K. [ABSTRACT FROM AUTHOR]

Abstract: Pressure dependent Wide Angle X-ray Scattering (WAXS) is employed to analyse the interplay between the amorphous and the nanocrystalline phases of major ampullate spider silk from Nephila edulis in the (hindered) supercontracted state. By comparing the previously published macroscopic elastic modulus with the nanocrystal modulus it is possible to quantify the contribution of the nanocrystals and the amorphous phase to the mechanical properties. From the detected shifts of the diffraction peaks the compression modulus of the nanocrystals is deduced and proven to be highest in the (100)-direction of intra-sheet hydrogen bonds. This reflects the molecular architecture of the stacked β-sheeted H-bonds within the nanocrystals. In addition, it is found that pressure may increase the organization of the amorphous phase, enhancing a diffraction ring close to the (210) reflection peak. It is more pronounced in the supercontracted state since the internal stress is released and the structure can rearrange. [Copyright &y& Elsevier]

Electronic functionalities in materials from silicon to transition metal oxides are, to a large extent, controlled by defects and their relative arrangement. Outstanding examples are the oxides of cop-per, where defect order is correlated with their high superconduct-ing transition temperatures. The oxygen defect order can be highly inhomogeneous, even in optimal superconducting samples, which raises the question of the nature of the sample regions where the order does not exist but which nonetheless form the "glue" binding the ordered regions together. Here we use scanning X-ray microdiffraction (with a beam 300 nm in diameter) to show that for La2Cu04+y, the glue regions contain incommensurate modulated local lattice distortions, whose spatial extent is most pronounced for the best superconducting samples. For an underdoped single crystal with mobile oxygen interstitials in the spacer La202+y layers intercalated between the Cu02 layers, the incommensurate modu-lated local lattice distortions form droplets anticorrelated with the ordered oxygen interstitials, and whose spatial extent is most pronounced for the best superconducting samples. In this simplest of high temperature superconductors, there are therefore not one, but two networks of ordered defects which can be tuned to achieve optimal superconductivity. For a given stoichiometry, the highest transition temperature is obtained when both the ordered oxygen and lattice defects form fractal patterns, as opposed to appearing in isolated spots. We speculate that the relationship between material complexity and superconducting transition temperature Tc is actually underpinned by a fundamental relation between Tc and the distribution of ordered defect networks sup-ported by the materials. [ABSTRACT FROM AUTHOR]

Abstract: A new method for the quantification of X-ray fluorescence (XRF) was derived based on the fundamental parameter method (FPM). The FPM equations were adapted to accommodate the special case of confocal nano-XRF, i.e. X-ray nano-beam excitation coupled with confocal detection, taking into account the special characteristics of the detector channel polycapillary. A thorough error estimation algorithm based on the Monte Carlo method was applied, producing a detailed analysis of the uncertainties of the quantification results. The new FPM algorithm was applied on confocal nano-XRF data obtained from cometary dust returned by NASA''s Stardust mission, recorded at beamline ID13 of the European Synchrotron Radiation Facility. [Copyright &y& Elsevier]

An X-ray scanning imaging technique using the integrated intensity of the small-angle X-ray scattering (SAXS) signal is presented. The technique is based on two-dimensional scanning of a thin sample section with an X-ray microbeam, collecting SAXS patterns at every scanning step using a two-dimensional detector. The integrated intensity within pre-defined regions of interest of the SAXS patterns is used to image bulk nanostructural features in the specimen with micrometre resolution which are usually not accessible by other methods such as light microscopy or scanning electron microscopy. The possibilities and limitations of the method are discussed with particular emphasis on the sources of contrast in the SAXS region for three biological specimens: cortical bone, eggshell and hair. Two main sources of image contrast are identified in the form of orientation effects for strongly anisotropic systems like cortical bone and differences in the local volume fraction of the scattering entities in eggshell. Moreover, other parameters than the integrated intensity can be quantitatively deduced from the SAXS patterns, for instance, the mean thickness of mineral platelets in bone or the strain distributions in a hair deformed plastically by microindentation. [ABSTRACT FROM AUTHOR]