Predictivity of the clock drawing test in the acute phase of cerebrovascular diseases on cognitive decline at a 6-month neuropsychological evaluation.

INTRODUCTION: We showed that the Clock Drawing Test (CDT) performed during the acute phase of cerebrovascular diseases predicted worsening of cognitive function defined based on a clinical judgement at a 3-month follow-up. The aim of this study was to verify the predictivity of the CDT on the worsening of cognitive status assessed with an extensive neuropsychological evaluation 6 months after the acute event. METHODS: Patients with a stroke or transient ischemic attack underwent a baseline clinical, neuroimaging, and neuropsychological assessment, including the CDT. Premorbid cognitive status was evaluated by means of the Clinical Dementia Rating scale. Between 6 and 7 months after the acute event, all patients underwent a neuropsychological evaluation that included tests for executive function, attention, language, memory, and visuospatial abilities. RESULTS: Fifty patients (29 males; mean age 72.2 years) were enrolled: 28 (56%) had no premorbid cognitive impairment, 15 (30%) had premorbid mild cognitive impairment (MCI), and 4 (8%) had premorbid dementia; for 3 patients, evaluation of premorbid status was not available. At follow-up, 11 (22%) had no cognitive impairment, 28 (56%) were diagnosed with MCI, and 11 (22%) dementia. In patients who were non-demented before the event, on regression analysis, the score obtained at CDT was predictive of decline of cognitive status at the 6-month follow-up (OR 1.65; 95% CI 1.08-2.52). DISCUSSION: Our study confirms that administering the CDT during the acute phase of cerebrovascular diseases is informative with regard to the worsening of cognitive function after 6 months.

In Situ Multimodal 3D Chemical Imaging of a Hierarchically Structured Core@Shell Catalyst.

A Cu/ZnO/Al2O3@ZSM-5 core@shell catalyst active for one-step conversion of synthesis gas to dimethyl ether (DME) was imaged simultaneously and in situ using synchrotron-based micro X-ray fluorescence (µ-XRF), X-ray diffraction (µ-XRD), and scanning transmission X-ray microscopy (STXM) computed tomography (CT) with micrometer spatial resolution. An identical sample volume was imaged stepwise, first under oxidizing and reducing atmospheres (imitating calcination and activation processes), and then under model reaction conditions for DME synthesis (H2:CO:CO2 ratio of 16:8:1, up to 250 °C). The multimodal imaging methods offered insights into the active metal structure and speciation within the catalyst, and allowed imaging of both the catalyst core and zeolite shell in a single acquisition. Dispersion of nanosized Cu species was observed in the catalyst core during reduction, with formation of a metastable Cu+ phase at the core-shell interface. Under DME reaction conditions at 1 bar, the coexistence of Cu0 in the active catalyst core together with partially oxidized Cu species was unraveled. The zeolite shell and core-shell interface remained stable under all conditions, preserving the bifunctional nature of the catalyst. These observations are inaccessible using standard bulk techniques like X-ray absorption spectroscopy (XAS) and XRD, demonstrating the potential of multimodal in situ X-ray CT for characterization of hierarchically designed materials, which stand to benefit tremendously from such 3D spatially resolved measurements.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Vanadium K-edge XANES in vanadium-bearing model compounds: a full multiple scattering study.

A systematic study is presented on a set of vanadium-bearing model compounds, representative of the most common V coordination geometries and oxidation states, analysed by means of vanadium K-edge X-ray absorption near-edge spectroscopy calculations in the full multiple scattering (FMS) framework. Analysis and calibration of the free parameters of the theory under the muffin-tin approximation (muffin-tin overlap and interstitial potential) have been carried out by fitting the experimental spectra using the MXAN program. The analysis shows a correlation of the fit parameters with the V coordination geometry and oxidation state. By making use of this correlation it is possible to approach the study of unknown V-bearing compounds with useful preliminary information.

In Situ Ptychography of Heterogeneous Catalysts using Hard X-Rays: High Resolution Imaging at Ambient Pressure and Elevated Temperature.

A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.

Studying the surface reaction between NiO and Al2O3 via total reflection EXAFS (ReflEXAFS).

The reaction between NiO and (0001)- and (1102)-oriented Al2O3 single crystals has been investigated on model experimental systems by using the ReflEXAFS technique. Depth-sensitive information is obtained by collecting data above and below the critical angle for total reflection. A systematic protocol for data analysis, based on the recently developed CARD code, was implemented, and a detailed description of the reactive systems was obtained. In particular, for (1102)-oriented Al2O3, the reaction with NiO is almost complete after heating for 6 h at 1273 K, and an almost uniform layer of spinel is found below a mixed (NiO + spinel) layer at the very upmost part of the sample. In the case of the (0001)-oriented Al2O3, for the same temperature and heating time, the reaction shows a lower advancement degree and a residual fraction of at least 30% NiO is detected in the ReflEXAFS spectra.