Julio C. da Silva

Assessment of the 3 D Pore Structure and Individual Components of Preshaped Catalyst Bodies by X-Ray Imaging

Porosity in catalyst particles is essential because it enables reactants to reach the active sites and it enables products to leave the catalyst. The engineering of composite‐particle catalysts through the tuning of pore‐size distribution and connectivity is hampered by the inability to visualize structure and porosity at critical‐length scales. Herein, it is shown that the combination of phase‐contrast X‐ray microtomography and high‐resolution ptychographic X‐ray tomography allows the visualization and characterization of the interparticle pores at micro‐ and nanometer‐length scales. Furthermore, individual components in preshaped catalyst bodies used in fluid catalytic cracking, one of the most used catalysts, could be visualized and identified. The distribution of pore sizes, as well as enclosed pores, which cannot be probed by traditional methods, such as nitrogen physisorption and isotherm analysis, were determined.

Central domain deletions affect the SAXS solution structure and function of Yeast Hsp40 proteins Sis1 and Ydj1

BackgroundYdj1 and Sis1 are structurally and functionally distinct Hsp40 proteins of the yeast cytosol. Sis1 is an essential gene whereas the ydj1 gene is essential for growth at elevated temperatures and cannot complement sis1 gene deletion. Truncated polypeptides capable of complementing the sis1 gene deletion comprise the J-domain of either Sis1 or Ydj1 connected to the G/F region of Sis1 (but not Ydj1). Sis1 mutants in which the G/F was deleted but G/M maintained were capable of complementing the sis1 gene deletion.ResultsTo investigate the relevance of central domains on the structure and function of Ydj1 and Sis1 we prepared Sis1 constructs deleting specific domains. The mutants had decreased affinity for heated luciferase but were equally capable of stimulating ATPase activity of Hsp70. Detailed low resolution structures were obtained and the overall flexibility of Hsp40 and its mutants were assessed using SAXS methods. Deletion of either the G/M or the G/M plus CTDI domains had little impact on the quaternary structure of Sis1 analyzed by the SAXS technique. However, deletion of the ZFLR-CTDI changed the relative position of the J-domains in Ydj1 in such a way that they ended up resembling that of Sis1. The results revealed that the G/F and G/M regions are not the only flexible domains. All model structures exhibit a common clamp-like conformation.ConclusionsOur results suggest that the central domains, previously appointed as important features for substrate binding, are also relevant keeping the J-domains in their specific relative positions. The clamp-like architecture observed seems also to be favorable to the interactions of Hsp40 with Hsp70.

Mass Density and Water Content of Saturated Never-Dried Calcium Silicate Hydrates

Calcium silicate hydrates (C-S-H) are the most abundant hydration products in ordinary Portland cement paste. Yet, despite the critical role they play in determining mechanical and transport properties, there is still a debate about their density and exact composition. Here, the site-specific mass density and composition of C-S-H in hydrated cement paste are determined with nanoscale resolution in a nondestructive approach. We used ptychographic X-ray computed tomography in order to determine spatially resolved mass density and water content of the C-S-H within the microstructure of the cement paste. Our findings indicate that the C-S-H at the border of hydrated alite particles possibly have a higher density than the apparent inner-product C-S-H, which is contrary to the common expectations from previous works on hydrated cement paste.

Elementary signals in ptychography

Ptychographic imaging has gained popularity for its high resolving power and sensitivity as well as for its ability to map simultaneously the samples complex-valued refractive index and the illumination. Yet, despite significant progress that allows for reliable practical implementation, some of the techniques fundamentals remain poorly understood, and oftentimes successful data acquisition is either overly conservative or relies more on experimenters experience than on rational data acquisition strategies. Here, we propose a theoretical framework of ptychography, which is based on Gabors notion of decomposition into elementary signals and the concept of frames. We demonstrate how this framework can straightforwardly be used to derive sampling requirements or to provide arguments on how to optimize the ptychographic scan. More generally, our theoretical framework can serve as a bridge between the experimental technique and the rich and well established mathematical disciplines of wavelets decomposition and spectrogram analysis.

Efficient correction of wavefront inhomogeneities in X-ray holographic nanotomography by random sample displacement

In X-ray tomography, ring-shaped artifacts present in the reconstructed slices are an inherent problem degrading the global image quality and hindering the extraction of quantitative information. To overcome this issue, we propose a strategy for suppression of ring artifacts originating from the coherent mixing of the incident wave and the object. We discuss the limits of validity of the empty beam correction in the framework of a simple formalism. We then deduce a correction method based on two-dimensional random sample displacement, with minimal cost in terms of spatial resolution, acquisition, and processing time. The method is demonstrated on bone tissue and on a hydrogen electrode of a ceramic-metallic solid oxide cell. Compared to the standard empty beam correction, we obtain high quality nanotomography images revealing detailed object features. The resulting absence of artifacts allows straightforward segmentation and posterior quantification of the data

High-energy cryo x-ray nano-imaging at the ID16A beamline of ESRF

The ID16A beamline at ESRF offers unique capabilities for X-ray nano-imaging, and currently produces the worlds brightest high energy diffraction-limited nanofocus. Such a nanoprobe was designed for quantitative characterization of the morphology and the elemental composition of specimens at both room and cryogenic temperatures. Billions of photons per second can be delivered in a diffraction-limited focus spot size down to 13 nm. Coherent X-ray imaging techniques, as magnified holographic-tomography and ptychographic-tomography, are implemented as well as X-ray fluorescence nanoscopy. We will show the latest developments in coherent and spectroscopic X-ray nanoimaging implemented at the ID16A beamline

Ptychographic nanotomography at the Swiss Light Source

Ptychography combines elements of scanning probe microscopy with coherent diffractive imaging and provides a robust high-resolution imaging technique. The extension of X-ray ptychography to 3D provides nanoscale maps with quantitative contrast of the sample complex-valued refractive index. We present here progress in reconstruction and post-processing algorithms for ptychographic nanotomography, as well as outline advances in the implementation and development of dedicated instrumentation for fast and precise 3D scanning at the Swiss Light Source. Compared to the first demonstration in 2010, such developments have allowed a dramatic improvement in resolution and measurement speed, with direct impact in the application of the technique for biology and materials science. We showcase the technique by detailing the measurement and reconstruction of a fossilized dispersed spore.

High energy near- and far-field ptychographic tomography at the ESRF

In high-resolution tomography, one needs high-resolved projections in order to reconstruct a high-quality 3D map of a sample. X-ray ptychography is a robust technique which can provide such high-resolution 2D projections taking advantage of coherent X-rays. This technique was used in the far-field regime for a fair amount of time, but it can now also be implemented in the near-field regime. In both regimes, the technique enables not only high-resolution imaging, but also high sensitivity to the electron density of the sample. The combination with tomography makes 3D imaging possible via ptychographic X-ray computed tomography (PXCT), which can provide a 3D map of the complex-valued refractive index of the sample. The extension of PXCT to X-ray energies above 15 keV is challenging, but it can allow the imaging of object opaque to lower energy. We present here the implementation and developments of high-energy near- and far-field PXCT at the ESRF.