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ObjectiveThe novel picture archiving and communication system (PACS), compatible with virtual reality (VR) software, displays cross-sectional images in VR. VR magnetic resonance cholangiopancreatography (MRCP) was tested to improve the anatomical understanding and intraoperative performance of minimally invasive cholecystectomy (CHE) in surgical trainees.DesignWe used an immersive VR environment to display volumetric MRCP data (Specto VRTM). First, we evaluated the tolerability and comprehensibility of anatomy with a validated simulator sickness questionnaire (SSQ) and examined anatomical landmarks. Second, we compared conventional MRCP and VR MRCP by matching three-dimensional (3D) printed models and identifying and measuring common bile duct stones (CBDS) using VR MRCP. Third, surgical trainees prepared for CHE with either conventional MRCP or VR MRCP, and we measured perioperative parameters and surgical performance (validated GOALS score).SettingThe study was conducted out at Clarunis, University Center for Gastrointestinal and Liver Disease, Basel, Switzerland.ParticipantsFor the first and second study step, doctors from all specialties and years of experience could participate. In the third study step, exclusively surgical trainees were included. Of 74 participating clinicians, 34, 27, and 13 contributed data to the first, second, and third study phases, respectively.ResultsAll participants determined the relevant biliary structures with VR MRCP. The median SSQ score was 0.75 (IQR: 0, 3.5), indicating good tolerability. Participants selected the corresponding 3D printed model faster and more reliably when previously studying VR MRCP compared to conventional MRCP: We obtained a median of 90 s (IQR: 55, 150) and 72.7% correct answers with VR MRCP versus 150 s (IQR: 100, 208) and 49.6% correct answers with conventional MRCP, respectively (p

Alectinib is a standard initial treatment for patients with advanced anaplastic lymphoma kinase (ALK) rearranged non-small-cell lung cancer (NSCLC). The current study analyzed a prospective cohort of 24 consecutive alectinib-treated patients and controls in order to comprehensively characterize longitudinal erythrocyte changes under treatment with ALK inhibitors. Upon starting alectinib, all examined patients developed reticulocytosis and abnormal erythrocyte morphology with anisocytosis and a predominance of acanthocytes (64% of red blood cells on average, range 36–100%) in the peripheral blood smear within approximately 2 weeks. Changes were accompanied by a gradual reduction in Eosin-5-maleimide (EMA) binding, which became pathologic (ANK1, EPB42, SLC4A1, SPTA1, or SBTB genes. The direct Coombs test was also negative in 11/11 tested cases. Besides, anemia, increased LDH, and increased bilirubin were noted in a fraction of patients only, ranging between 42 and 68%. Furthermore, haptoglobin decreases were infrequent, occurring in approximately 1/3 of cases only, and mild, with an average value of 0.93 g/L within the normal range of 0.3–2 g/dL, suggesting that hemolysis occurred predominantly in the extravascular compartment, likely due to splenic trapping of the deformed erythrocytes. These changes showed no association with progression-free survival under alectinib or molecular features, i.e., ALK fusion variant or TP53 status of the disease, and resolved upon a switch to an alternative ALK inhibitor. Thus, alectinib induces mild, reversible erythrocyte changes in practically all treated patients, whose most sensitive signs are aberrant red cell morphology in the peripheral smear, a pathologic EMA test, and reactive reticulocytosis. Frank hemolytic anemia is rare, but mild subclinical hemolysis is very frequent and poses differential-diagnostic problems. Alectinib can be continued under the regular control of hemolysis parameters, but the risk of long-term complications, such as cholelithiasis due to increased serum bilirubin in most patients, remains unclear at present.

Abstract A profound understanding of the solid/liquid interface is central in electrochemistry and electrocatalysis, as the interfacial properties ultimately determine the electro‐reactivity of a system. Although numerous electrochemical methods exist to characterize this interface under operating conditions, tools for the in‐situ observation of the surface chemistry, that is, chemical composition and oxidation state, are still scarce, and currently exclusively available at synchrotron facilities. Here, we demonstrate the ability of laboratory‐based near‐ambient pressure X‐ray photoelectron spectroscopy to track changes in oxidation states in‐situ with respect to the applied potential. In this proof‐of‐principle study with polycrystalline gold (Au) as the best‐studied electrochemical standard, we show that during the oxygen evolution reaction (OER), at high OER overpotentials, Au3+ governs the interfacial chemistry, while, at lower overpotentials, Au+ dominates.

Abstract Background Sepsis-induced immunosuppression is a frequent cause of opportunistic infections and death in critically ill patients. A better understanding of the underlying mechanisms is needed to develop targeted therapies. Circulating bile acids with immunosuppressive effects were recently identified in critically ill patients. These bile acids activate the monocyte G-protein coupled receptor TGR5, thereby inducing profound innate immune dysfunction. Whether these mechanisms contribute to immunosuppression and disease severity in sepsis is unknown. The aim of this study was to determine if immunosuppressive bile acids are present in endotoxemia and septic shock and, if so, which patients are particularly at risk. Methods To induce experimental endotoxemia in humans, ten healthy volunteers received 2 ng/kg E. coli lipopolysaccharide (LPS). Circulating bile acids were profiled before and after LPS administration. Furthermore, 48 patients with early (shock onset within 0.4 μg/kg/min) and 48 healthy age- and sex-matched controls were analyzed for circulating bile acids. To screen for immunosuppressive effects of circulating bile acids, the capability to induce TGR5 activation was computed for each individual bile acid profile by a recently published formula. Results Although experimental endotoxemia as well as septic shock led to significant increases in total bile acids compared to controls, this increase was mild in most cases. By contrast, there was a marked and significant increase in circulating bile acids in septic shock patients with severe liver failure compared to healthy controls (61.8 µmol/L vs. 2.8 µmol/L, p = 0.0016). Circulating bile acids in these patients were capable to induce immunosuppression, as indicated by a significant increase in TGR5 activation by circulating bile acids (20.4% in severe liver failure vs. 2.8% in healthy controls, p = 0.0139). Conclusions Circulating bile acids capable of inducing immunosuppression are present in septic shock patients with severe liver failure. Future studies should examine whether modulation of bile acid metabolism can improve the clinical course and outcome of sepsis in these patients. Graphical abstract

Abstract NaTi2(PO4)3 (NTP) and Na0.44MnO2 (NMO), and their derivatives, have emerged as the most promising materials for aqueous Na‐ion batteries. For both, NTP and NMO, avoiding the evolution of hydrogen and oxygen is found to be mandatory in order to mitigate material dissolution. Intriguingly, however, no direct determination of the hydrogen and oxygen evolution reactions (HER and OER) has yet been carried out. Using differential electrochemical mass spectrometry (DEMS) we directly identify the onset potentials for the HER and OER. Surprisingly, the potential window is found to be significantly smaller than suggested by commonly employed cyclic voltammetry measurements. CO2 evolution, upon decomposition of carbon black, is observed at an onset potential of 1.61 VRHE, which is 0.25 V more cathodic than the OER for the NMO electrode. Our results show that the state‐of‐the‐art carbon additive plays a crucial role in the stability of the positive NMO electrode in the ion battery.

For the direct reduction of CO2 and H2O in solid oxide electrolysis cells (SOECs) with cermet electrodes toward methane, a fundamental understanding of the role of elemental carbon as a key intermediate within the reaction pathway is of eminent interest. The present synchrotron-based in situ near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) study shows that alloying of Ni/yttria-stabilized-zirconia (YSZ) cermet electrodes with Cu can be used to control the electrochemical accumulation of interfacial carbon and to optimize its reactivity toward CO2. In the presence of syngas, sufficiently high cathodic potentials induce excess methane on the studied Ni/yttria-stabilized-zirconia (YSZ)-, NiCu/YSZ- and Pt/gadolinium-doped-ceria (GDC) cermet systems. The hydrogenation of carbon, resulting from CO activation at the triple-phase boundary of Pt/GDC, is most efficient.

Excellent, self‐improving sodiation rate capabilities in combination with high capacity retention upon galvanostatic charge/discharge cycling are found for oxygen‐deficient, carburized, and self‐organized titanium dioxide (TiO2−x) nanotubes (NTs). The sodiation mechanism is attributed to the formation of an acicular surface film as the active storage material with sodium (Na) peroxide (Na2O2) being the main component. Whether the proposed surface chemistry is unique for TiO2 NTs or serves as a common scheme for Na‐ion storage at metal oxide surfaces, in general, is not clear by now. Herein, three different materials, titanium(IV) oxide in the anatase and rutile phase and molybdenum(IV) oxide, are investigated in a planar electrode geometry toward their capability for Na‐ion storage. It is shown that all three materials under investigation demonstrate a significant progression of capacity increase upon cycling in combination with the formation of a Na‐oxide containing surface film. These “self‐improving” characteristics are found to significantly enhance the Na‐ion storage performance of the electrodes during long‐term galvanostatic cycling in a Na‐containing electrolyte.

Abstract Long term galvanostatic charge/discharge cycling of oxygen deficient, carburized and self‐organized titanium dioxide (TiO2) nanotubes (NTs) in sodium ion (Na) batteries (SIBs) are subject to a significant self‐improving charge storage behavior. Surface reactions upon sodiation of carburized NTs form acicular surface films that can be reversibly cycled. We show that, alongside organic species from the decomposition of the electrolyte, mainly inorganic compounds, such as Na2O2 and Na2CO3, are the main constituents. These components possess a characteristic acicular morphology. Na2O2 is found to form upon sodiation and converted to NaO2 upon desodiation. This, in combination with its pseudo‐capacitive charge storage characteristics, explains the excellent rate capability measured for TiO2‐x‐C NTs. The observed high reversibility of this surface chemistry is also essential for the fast kinetics and the high capacity retention found in the system. Our findings point to a more general Na‐ion storage mechanism, that is potentially relevant to other transition metal oxides also.

Abstract Small organic acids, such as formic or acetic acid, which are well‐known products of the electrochemical CO2 reduction reaction, are often not further reduceable to their respective alcohols. Alcohols are well‐desired chemicals and useful as fuels, since they can be easily purified and provide a high energy density. Here, we present a combined electrochemical, differential electrochemical mass spectrometry (DEMS), and nuclear magnetic resonance spectroscopy (NMR) study, providing insight in the electro‐reduction of formic acid on Mo2C electrodes, and the corresponding formation of notable amounts of methanol, with a Faraday efficiency of ∼27 % at a high steady state current density of –0.3 mA/cm2 compared to other formic acid electroreduction catalysts, such as Pb or Sn. Intriguingly, we find that formic and acetic acid readily form on native oxide covered Mo2C surfaces in air and especially in humid CO2 atmosphere. We realize that the thin native oxide layer that is ubiquitously present on these electrodes is the key factor for the activation of CO2 and the corresponding formation of formic and acetic acid at the solid/gas interface. Subsequent electrochemical reduction of these two acids at the solid/liquid interface proceeds through direct formation of their respective alcohols. The activity toward organic acid reduction on Mo2C catalysts can therefore be enhanced by their adsorption properties at the surface and not necessarily through inhibition of the HER, which is exceptional and points to a general strength of compound catalysts for organic acid reduction and CO2 activation.

A 14-day randomized controlled study with a parallel design was conducted with 80 healthy participants. Intervention groups I (IG1) and II (IG2) received a defined background diet and consumed a smoothie enriched with either 15 g of Chlorella dry weight (d.w.) or 15 g of Microchloropsis d.w. daily. Control group II (CG2) received a defined background diet without the smoothie. Control group I (CG1) received neither. Blood samples and 24-h urine were collected at the beginning and the end of the study. Serum concentrations of 25-hydroxyvitamin D3, vitamin D3, selenium, iron, ferritin, transferrin saturation, total cholesterol, low-density lipoprotein (LDL) cholesterol, high-density lipoprotein (HDL) cholesterol, non-HDL cholesterol and the LDL-cholesterol/HDL cholesterol ratio decreased in IG1 (p < 0.05), while 25-hydroxyvitamin D2 increased (p < 0.05). In IG2, vitamin D3, 25-hydroxyvitamins D2 and D3 decreased (p < 0.05), while concentrations of fatty acids C20:5n3 and C22:5n3 increased. Serum and urine uric acid increased in IG1 and IG2 (p < 0.05). Microchloropsis is a valuable source of n3 fatty acids, as is Chlorella of vitamin D2. Regular consumption of Chlorella may affect the iron and selenium status negatively but may impact blood lipids positively. An elevated uric acid concentration in blood and urine following the regular consumption of microalgae poses potential risks for human health.

The use of an activated carbon based quasi-reference electrode for in situ electrochemical scanning tunneling microscopy was found to allow investigations of electrode/electrolyte interfaces under realistic electrochemical reaction conditions. The implementation of purely inert porous carbon electrode materials, both as reference and counter electrode, ensures a stable reference electrode potential over a wide range of temperatures and in different electrolytes, which renders this electrode ‘universal’. Furthermore, the high surface area carbon can reduce and even eliminate contaminations that might be present in the electrolyte. Activated carbon electrodes can therefore generally contribute to more reliable electrochemical measurements when investigating electrochemical reactions under complex experimental conditions, where the use of classical secondary reference electrodes is impossible or impractical. This is often the case when electrochemistry is combined with in situ interface analytics. Keywords: Electrochemical scanning tunneling microscopy, Quasi-reference electrode, Activated carbon

The solvated molecular salt, C13H30N3+·C20H36BSi4−·C4H10O, was obtained by the reaction of trimethylsilylethyne with boron trichloride in the presence of tert-butyllithium, followed by ion metathesis. The cation exhibits positional disorder and one of the Me3Si groups shows rotational disorder. No significant directional intermolecular interactions are observed.