Multi‐Method Characterization of the High‐Entropy Spinel Oxide Mn0.2_{0.2}Co0.2_{0.2}Ni0.2_{0.2}Cu0.2_{0.2}Zn0.2_{0.2}Fe2_{2}O4_{4}: Entropy Evidence, Microstructure, and Magnetic Properties

The novel spinel Cu0.2Co0.2Mn0.2Ni0.2Zn0.2Fe2O4 comprising six transition metal cations was successfully prepared by a solution-combustion method followed by distinct thermal treatments. The entropic stabilization of this hexa-metallic material is demonstrated using in situ high temperature powder X-ray diffraction (PXRD) and directed removal of some of the constituting elements. Thorough evaluation of the PXRD data yields sizes of coherently scattering domains in the nanometre-range. Transmission electron microscopy based methods support this finding and indicate a homogeneous distribution of the elements in the samples. The combination of 57Fe Mössbauer spectroscopy with X-ray absorption near edge spectroscopy allowed determination of the cation occupancy on the tetrahedral and octahedral sites in the cubic spinel structure. Magnetic studies show long-range magnetic exchange interactions which are of ferri- or ferromagnetic nature with an exceptionally high saturation magnetization in the range of 92–108 emu g−1 at low temperature, but also an anomaly in the hysteresis of a sample calcined at 500 °C

Luminescent silver nanoclusters decorated on ZnO tetrapods: a detailed understanding of their role in photoluminescence features

Optical spectroscopic measurements are conducted on luminescent silver nanocluster (AgNC) decorated ZnO tetrapods (ZnO Tp), AgNC@ZnO Tp, synthesized via a colloidal route. Their properties are compared with those of the corresponding AgNC and ZnO Tp to understand their impact on the photoluminescence (PL). Raman spectroscopy reveals the high structural integrity of the ZnO structure in the AgNC@ZnO Tp. PL analysis of the ZnO Tp shows a well-resolved near band edge emission and a green band comprised by the overlapping of at least three emitting optical centres. The addition of AgNC to ZnO Tp in the hybrid material enhances the emission from ZnO surface states. The recombination of the AgNC in water solution is dominated by a red emission band peaking at ∼1.9 eV and the PL excitation spectra monitored at the band maximum reveal that the red PL of AgNC is preferentially populated by well-defined excitation bands corresponding to discrete electronic transitions of the NCs. Yet, a shift to lower energies of the AgNC emission occurs in the AgNC@ZnO Tp hybrid when excited with energies below the ZnO bandgap, while for energies above this value no emission from the AgNC was observed, with the ZnO-related recombination dominating the spectra. A gradual loss in the PL intensity of the AgNC is observed in the hybrid with increasing time, which is consistent with their coalescence to transform into larger Ag nanoparticles (NPs) on the tetrapod surface, as revealed by confocal microscopy.publishe

Advanced Hybrid GaN/ZnO Nanoarchitectured Microtubes for Fluorescent Micromotors Driven by UV Light

The development of functional microstructures with designed hierarchical and complex morphologies and large free active surfaces offers new potential for improvement of the pristine microstructures properties by the synergistic combination of microscopic as well as nanoscopic effects. In this contribution, dedicated methods of transmission electron microscopy (TEM) including tomography are used to characterize the complex hierarchically structured hybrid GaN/ZnO:Au microtubes containing a dense nanowire network on their interior. The presence of an epitaxially stabilized and chemically extremely stable ultrathin layer of ZnO on the inner wall of the produced GaN microtubes is evidenced. Gold nanoparticles initially trigger the catalytic growth of solid solution phase (Ga1– xZnx)(N1– xOx) nanowires into the interior space of the microtube, which are found to be terminated by AuGa-alloy nanodots coated in a shell of amorphous GaOx species after the hydride vapor phase epitaxy process. The structural characterization suggests that this hierarchical design of GaN/ZnO microtubes could offer the potential to exhibit improved photocatalytic properties, which are initially demonstrated under UV light irradiation. As a proof of concept, the produced microtubes are used as photocatalytic micromotors in the presence of hydrogen peroxide solution with luminescent properties, which are appealing for future environmental applications and active matter fundamental studies. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Elucidating catalytic sites governing the performance toward the hydrogen evolution reaction in ternary nitride electrocatalysts

Proton exchange membrane electrolyzers are considered the most advanced devices for producing green hydrogen by water electrolysis. Their development requires catalytic materials that are stable under acidic conditions and drive the hydrogen evolution reaction (HER) forward efficiently which makes research into the identification of the catalytic sites important. We report that free-standing Co2Mo3N and Ni2Mo3N achieve overpotentials of 149 ± 8 and 158 ± 10 mV (in 0.5 M H2SO4) at a benchmark current density of 10 mA cm–2. Both nitrides remained stable and consistently deliver current densities >500 mA cm–2 at a potential as low as 308 ± 22 mV when they were immobilized on nickel foam. Replacing Ni for Fe in Ni2Mo3N leads to FexNi2–xMo3N (0.5 ≤ x ≤ 1.25) that show a decrease in catalytic activity as the value of x increases which confirms that Ni (rather than Mo and N) sites are catalytically active. The X-ray photoelectron spectroscopy data additionally suggests that preserving the low oxidation states of transition metals in the nitrides is important for achieving good catalytic performance toward the HER in acidic electrolytes

A new imaging tool for realtime measurement of flow velocity in intracranial aneurysms

With modern imaging modalities of the brain a significant number of unruptured aneurysms are detected. However, not every aneurysm is prone to rupture. Because treatment morbidity is about 10% it is crucial to identify unstable aneurysms for which treatment should be discussed. Recently, new imaging tools allow analysis of flow dynamics and wall stability have become available. It seems that they might provide additional data for better risk profiling. In this study we present a new imaging tool for analysis of flow dynamics, which calculates fluid velocity in an aneurysm (Phillips Electronics, N.V.). It may identify regions with high flow and calculate flow reduction after stenting of aneurysms. Contrast is injected with a stable injection speed of 2 mL/sec for 3 sec. Two clinical cases are illustrated. Velocity in aneurysms and areas of instability can be identified and calculated during angiography in real-time. After stenting and flow diverter deployment flow reduction in the internal carotid aneurysm was reduced by 60% and there was a reduction of about 65% in the posterior cerebral artery in the second case we are reporting. The dynamic flow software calculates the flow profile in the aneurysm immediately after contrast injection. It is a real-time, patient specific tool taking into account systole, diastole and flexibility of the vasculature. These factors are an improvement as compared to current models of computational flow dynamics. We think it is a highly efficient, user friendly tool. Further clinical studies are on their way

Periprocedural safety and outcome after pump implantation for intravenous treprostinil administration in patients with pulmonary arterial hypertension

Methods!#!In this retrospective observational study, we analyzed all patients with pulmonary arterial hypertension undergoing LenusPro® pump implantation between November 2013 and October 2019 at our center. Periprocedural safety was assessed by describing all complications that occurred within 28 days after surgery; complications that occurred later were described to assess long-term safety. Clinical outcomes were measured by comparison of clinical parameters and echocardiographic measurements of right ventricular function from baseline to 6-months-follow-up.!##!Results!#!Fifty-four patients underwent LenusPro® pump implantation for intravenous treprostinil treatment during the investigation period. Periprocedural complications occurred in 5 patients; the only anesthesia-related complication (right heart failure with recovery after prolonged intensive care and death in the further course) occurred in the only patient who underwent general anesthesia. All other patients underwent local anesthesia with or without short-acting (analgo-) sedation. Eighteen long-term complications occurred in 15 patients, most notably pump pocket or catheter related problems. Transplant-free survival rates at 1, 2, and 3 years were 77 %, 56 %, and 48 %, respectively.!##!Conclusions!#!Subcutaneous pump implantation under local anesthesia and conscious analgosedation while avoiding intubation and mechanical ventilation is feasible in patients with advanced PAH. Controlled studies are needed to determine the safest anesthetic approach for this procedure.!##!Background/objectives!#!Intravenous treprostinil treatment via a fully implantable pump is a treatment option for patients with advanced pulmonary arterial hypertension. However, there is no consensus on the preferred anesthetic approach for the implantation procedure. Primary objective was to assess periprocedural safety with particular attention to feasibility of local anesthesia and conscious analgosedation instead of general anesthesia. Long-term safety and clinical outcomes were secondary endpoints

Synthesis, crystal structure, and selected properties of [Au(S2CNH2)2]SCN: a precursor for gold macro‐needles consisting of gold nanoparticles glued by graphitic carbon nitride

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S$_2$CNH$_2$)$_2$]SCN, which avoids disproportionation of the AuI salt used as a starting material. In the crystal structure, the two crystallographically independent AuIII centers are in a square-planar environment of two S$_2$CNH$_2$ ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)$_2$N. $^{13}$C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles

Advanced Hybrid GaN/ZnO Nanoarchitectured Microtubes for Fluorescent Micromotors Driven by UV Light

The development of functional microstructures with designed hierarchical and complex morphologies and large free active surfaces offers new potential for improvement of the pristine microstructures properties by the synergistic combination of microscopic as well as nanoscopic effects. In this contribution, dedicated methods of transmission electron microscopy (TEM) including tomography are used to characterize the complex hierarchically structured hybrid GaN/ZnO:Au microtubes containing a dense nanowire network on their interior. The presence of an epitaxially stabilized and chemically extremely stable ultrathin layer of ZnO on the inner wall of the produced GaN microtubes is evidenced. Gold nanoparticles initially trigger the catalytic growth of solid solution phase (Ga1– xZnx)(N1– xOx) nanowires into the interior space of the microtube, which are found to be terminated by AuGa-alloy nanodots coated in a shell of amorphous GaOx species after the hydride vapor phase epitaxy process. The structural characterization suggests that this hierarchical design of GaN/ZnO microtubes could offer the potential to exhibit improved photocatalytic properties, which are initially demonstrated under UV light irradiation. As a proof of concept, the produced microtubes are used as photocatalytic micromotors in the presence of hydrogen peroxide solution with luminescent properties, which are appealing for future environmental applications and active matter fundamental studies. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Comparative Analysis of Gene Expression in Fibroblastic Foci in Patients with Idiopathic Pulmonary Fibrosis and Pulmonary Sarcoidosis

Background: Fibroblastic foci (FF) are characteristic features of usual interstitial pneumonia (UIP)/idiopathic pulmonary fibrosis (IPF) and one cardinal feature thought to represent a key mechanism of pathogenesis. Hence, FF have a high impact on UIP/IPF diagnosis in current guidelines. However, although less frequent, these histomorphological hallmarks also occur in other fibrotic pulmonary diseases. Currently, there is therefore a gap in knowledge regarding the underlying molecular similarities and differences of FF in different disease entities. Methods: In this work, we analyzed the compartment-specific gene expression profiles of FF in IPF and sarcoidosis in order to elucidate similarities and differences as well as shared pathomechanisms. For this purpose, we used laser capture microdissection, mRNA and protein expression analysis. Biological pathway analysis was performed using two different gene expression databases. As control samples, we used healthy lung tissue that was donated but not used for lung transplantation. Results: Based on Holm Bonferroni corrected expression data, mRNA expression analysis revealed a significantly altered expression signature for 136 out of 760 genes compared to healthy controls while half of these showed a similar regulation in both groups. Immunostaining of selected markers from each group corroborated these results. However, when comparing all differentially expressed genes with the fdr-based expression data, only 2 of these genes were differentially expressed between sarcoidosis and IPF compared to controls, i.e., calcium transport protein 1 (CAT1) and SMAD specific E3 ubiquitin protein ligase 1 (SMURF1), both in the sarcoidosis group. Direct comparison of sarcoidosis and IPF did not show any differentially regulated genes independent from the statistical methodology. Biological pathway analysis revealed a number of fibrosis-related pathways pronounced in IPF without differences in the regulatory direction. Conclusions: These results demonstrate that FF of end-stage IPF and sarcoidosis lungs, although different in initiation, are similar in gene and protein expression, encouraging further studies on the use of antifibrotic agents in sarcoidosis