Intermetallic Cobalt Indium Nanoparticles as Oxygen Evolution Reaction Precatalyst: A Non-Leaching p-Block Element.

Merely all transition-metal-based materials reconstruct into similar oxyhydroxides during the electrocatalytic oxygen evolution reaction (OER), severely limiting the options for a tailored OER catalyst design. In such reconstructions, initial constituent p-block elements take a sacrificial role and leach into the electrolyte as oxyanions, thereby losing the ability to tune the catalyst's properties systematically. From a thermodynamic point of view, indium is expected to behave differently and should remain in the solid phase under alkaline OER conditions. However, the structural behavior of transition metal indium phases during the OER remains unexplored. Herein, are synthesized intermetallic cobalt indium (CoIn3) nanoparticles and revealed by in situ X-ray absorption spectroscopy and scanning transmission microscopy that they undergo phase segregation to cobalt oxyhydroxide and indium hydroxide. The obtained cobalt oxyhydroxide outperforms a metallic-cobalt-derived one due to more accessible active sites. The observed phase segregation shows that indium behaves distinctively differently from most p-block elements and remains at the electrode surface, where it can form lasting interfaces with the active metal oxo phases.

Effect of Surface-Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction.

As the kinetically demanding oxygen evolution reaction (OER) is crucial for the decarbonization of our society, a wide range of (pre)catalysts with various non-active-site elements (e.g., Mo, S, Se, N, P, C, Si…) have been investigated. Thermodynamics dictate that these elements oxidize during industrial operation. The formed oxyanions are water soluble and thus predominantly leach in a reconstruction process. Nevertheless, recently, it was unveiled that these thermodynamically stable (oxy)anions can adsorb on the surface or intercalate in the interlayer space of the active catalyst. There, they tune the electronic properties of the active sites and can interact with the reaction intermediates, changing the OER kinetics and potentially breaking the persisting OER *OH/*OOH scaling relations. Thus, the addition of (oxy)anions to the electrolyte opens a new design dimension for OER catalysis and the herein discussed observations deepen the understanding of the role of anions in the OER.

Facile Access to an Active γ-NiOOH Electrocatalyst for Durable Water Oxidation Derived From an Intermetallic Nickel Germanide Precursor.

Identifying novel classes of precatalysts for the oxygen evolution reaction (OER by water oxidation) with enhanced catalytic activity and stability is a key strategy to enable chemical energy conversion. The vast chemical space of intermetallic phases offers plenty of opportunities to discover OER electrocatalysts with improved performance. Herein we report intermetallic nickel germanide (NiGe) acting as a superior activity and durable Ni-based electro(pre)catalyst for OER. It is produced from a molecular bis(germylene)-Ni precursor. The ultra-small NiGe nanocrystals deposited on both nickel foam and fluorinated tin oxide (FTO) electrodes showed lower overpotentials and a durability of over three weeks (505 h) in comparison to the state-of-the-art Ni-, Co-, Fe-, and benchmark NiFe-based electrocatalysts under identical alkaline OER conditions. In contrast to other Ni-based intermetallic precatalysts under alkaline OER conditions, an unexpected electroconversion of NiGe into γ-NiIII OOH with intercalated OH- /CO3 2- transpired that served as a highly active structure as shown by various ex situ methods and quasi in situ Raman spectroscopy.

Titanium-catalyzed reductive umpolung reactions with a metal-free terminal reducing agent.

A new method for titanium-catalyzed reductive umpolung reactions is reported that overcomes the traditional requirement for a stoichiometric metallic reductant. With N,N'-disilylated tetramethyldihydropyrazine as a potent organic reducing agent, reductive carbonyl-nitrile, enone-acrylonitrile and pinacol coupling reactions can be achieved in good yields and stereoselectivities. [Cp2TiI2] is a superior catalyst to [Cp2TiCl2], which is rationalized by a faster generation of the active catalyst [Cp2TiI]. A mechanism is proposed that is in agreement with the experimental results.

[Gender differences and inflammatory bowel disease]. / Geschlechtsspezifische Unterschiede in der Behandlungsrealität von Patientinnen und Patienten mit chronisch-entzündlichen Darmerkrankungen (CED).

This review focuses on the gender and sex dimorphic disease profile and treatment reality of patients suffering from inflammatory bowel diseases (IBD). It provides an overview of gender-specific differences in the disease course, medical and surgical therapy as well as psychosocial aspects of IBD.

Challenges for Hybrid Water Electrolysis to Replace the Oxygen Evolution Reaction on an Industrial Scale.

To enable a future society based on sun and wind energy, transforming electricity into chemical energy in the form of fuels is crucial. This transformation can be achieved in an electrolyzer performing water splitting, where at the anode, water is oxidized to oxygen-oxygen evolution reaction (OER)-to produce protons and electrons that can be combined at the cathode to form hydrogen-hydrogen evolution reaction (HER). While hydrogen is a desired fuel, the obtained oxygen has no economic value. A techno-economically more suitable alternative is hybrid water electrolysis, where value-added oxidation reactions of abundant organic feedstocks replace the OER. However, tremendous challenges remain for the industrial-scale application of hybrid water electrolysis. Herein, these challenges, including the higher kinetic overpotentials of organic oxidation reactions compared to the OER, the small feedstock availably and product demand of these processes compared to the HER (and carbon dioxide reduction), additional purifications costs, and electrocatalytic challenges to meet the industrially required activities, selectivities, and especially long-term stabilities are critically discussed. It is anticipated that this perspective helps the academic research community to identify industrially relevant research questions concerning hybrid water electrolysis.

Clinical implantation of 92 VACStents in the upper gastrointestinal tract of 50 patients-applicability and safety analysis of an innovative endoscopic concept.

Introduction: Endoscopic vacuum therapy (EVT) has emerged as a promising treatment option for upper gastrointestinal wall defects, offering benefits such as evacuation of secretions and removal of wound debris by suction, and reduction and healing of wound cavities to improve clinical outcomes. In contrast, covered stents have a high rate of migration and lack functional drainage, while endoluminal EVT devices obstruct the GI tract. The VACStent is a novel device that combines the benefits of EVT and stent placement. Its design features a fully covered Nitinol-stent within a polyurethane sponge cylinder, enabling EVT while maintaining stent patency. Methods: This study analyzes the pooled data from three different prospective study cohorts to assess the safe practicality of VACStent placement, complete leak coverage, and effective suction-treatment of esophageal leaks. By pooling the data, the study aims to provide a broader base for analysis. Results: In total, trans-nasal derivation of the catheter, suction and drainage of secretion via vacuum pump were performed without any adversity. In the pooled study cohort of 92 VACStent applications, the mean stent indwelling time was 5.2 days (range 2-8 days) without any dislocation of the device. Removal of the VACStent was done without complication, in one case the sponge was lost but subsequently fully preserved. Minor local erosions and bleeding and one subsequent hemostasis were recorded unfrequently during withdrawal of the device (5.4%, 5/92) but no perforation or pressure ulcer. Despite a high heterogeneity regarding primary disease and pretreatments a cure rate of 76% (38/50 patients) could be achieved. Discussion: In summary, insertion and release procedure was regarded as easy and simple with a low potential of dislocation. The VACStent was well tolerated by the patient while keeping the drainage function of the sponge achieving directly a wound closure by continuous suction and improving the healing process. The implantation of the VACStent provides a promising new procedure for improved clinical treatment in various indications of the upper gastrointestinal wall, which should be validated in larger clinical studies.Clinical Trial Registration: Identifier [DRKS00016048 and NCT04884334].

Oxygen Evolution Activity of Amorphous Cobalt Oxyhydroxides: Interconnecting Precatalyst Reconstruction, Long-Range Order, Buffer-Binding, Morphology, Mass Transport, and Operation Temperature.

Nanocrystalline or amorphous cobalt oxyhydroxides (CoCat) are promising electrocatalysts for the oxygen evolution reaction (OER). While having the same short-range order, CoCat phases possess different electrocatalytic properties. This phenomenon is not conclusively understood, as multiple interdependent parameters affect the OER activity simultaneously. Herein, a layered cobalt borophosphate precatalyst, Co(H2 O)2 [B2 P2 O8 (OH)2 ]·H2 O, is fully reconstructed into two different CoCat phases. In contrast to previous reports, this reconstruction is not initiated at the surface but at the electrode substrate to catalyst interface. Ex situ and in situ investigations of the two borophosphate derived CoCats, as well as the prominent CoPi and CoBi identify differences in the Tafel slope/range, buffer binding and content, long-range order, number of accessible edge sites, redox activity, and morphology. Considering and interconnecting these aspects together with proton mass-transport limitations, a comprehensive picture is provided explaining the different OER activities. The most decisive factors are the buffers used for reconstruction, the number of edge sites that are not inhibited by irreversibly bonded buffers, and the morphology. With this acquired knowledge, an optimized OER system is realized operating in near-neutral potassium borate medium at 1.62 ± 0.03 VRHE yielding 250 mA cm-2 at 65 °C for 1 month without degrading performance.

Increased levels of anti-glycan antibodies in patients with cystic fibrosis.

BACKGROUND: The prevalence of Crohn's disease (CD) is increased in patients with cystic fibrosis (CF). Anti-Saccharomyces cerevisiae antibodies (ASCA) have been suggested as a screening tool to detect CD in CF. Recently, several new anti-glycan antibodies have been reported in CD. - MATERIALS AND METHODS: The sera of 119 CF patients of various age groups were prospectively screened for ASCA type IgG (gASCA), anti-laminaribioside carbohydrate IgG antibodies (ALCA), anti-chitobioside carbohydrate IgA antibodies (ACCA), and anti-mannobioside carbohydrate IgG antibodies (AMCA). The frequency of these anti-glycan antibodies was then compared in patients with CD, ulcerative colitis, rheumatoid arthritis and healthy volunteers. - RESULTS: A significant number of CF patients were positive for gASCA (51.3% (41.6-60.6)) and up to three other anti-glycan antibodies concurrently. Serum levels of anti-glycan antibodies in CF and CD were not related to parameters of inflammation. Despite the well-documented difference in clinical course between male and female CF patients no gender difference of anti-glycan antibodies was found. In contrast, there was a significant positive correlation between anti-glycan markers and age in CF patients. - CONCLUSIONS: Our findings demonstrate for the first time the increased frequency of a panel of anti-glycan antibodies in CF and provide a link between the presence of these serological biomarkers and patient's age. Anti-glycan antibody profiling may therefore become a valuable tool in the care of patients with CF.

Evolving Highly Active Oxidic Iron(III) Phase from Corrosion of Intermetallic Iron Silicide to Master Efficient Electrocatalytic Water Oxidation and Selective Oxygenation of 5-Hydroxymethylfurfural.

In a green energy economy, electrocatalysis is essential for chemical energy conversion and to produce value added chemicals from regenerative resources. To be widely applicable, an electrocatalyst should comprise the Earth's crust's most abundant elements. The most abundant 3d metal, iron, with its multiple accessible redox states has been manifold applied in chemocatalytic processes. However, due to the low conductivity of FeIII Ox Hy phases, its applicability for targeted electrocatalytic oxidation reactions such as water oxidation is still limited. Herein, it is shown that iron incorporated in conductive intermetallic iron silicide (FeSi) can be employed to meet this challenge. In contrast to silicon-poor iron-silicon alloys, intermetallic FeSi possesses an ordered structure with a peculiar bonding situation including covalent and ionic contributions together with conducting electrons. Using in situ X-ray absorption and Raman spectroscopy, it could be demonstrated that, under the applied corrosive alkaline conditions, the FeSi partly forms a unique, oxidic iron(III) phase consisting of edge and corner sharing [FeO6 ] octahedra together with oxidized silicon species. This phase is capable of driving the oxyge evolution reaction (OER) at high efficiency under ambient and industrially relevant conditions (500 mA cm-2 at 1.50 ± 0.025 VRHE and 65 °C) and to selectively oxygenate 5-hydroxymethylfurfural (HMF).

Intermetallic Fe6Ge5 formation and decay of a core-shell structure during the oxygen evolution reaction.

Herein, we report on intermetallic iron germanide (Fe6Ge5) as a novel oxygen evolution reaction (OER) precatalyst with a Tafel slope of 32 mV dec-1 and an overpotential of 272 mV at 100 mA cm-2 in alkaline media. Furthermore, we uncover the in situ formation of a core-shell like structure that slowly collapses under OER conditions.

A soft molecular 2Fe-2As precursor approach to the synthesis of nanostructured FeAs for efficient electrocatalytic water oxidation.

An unprecedented molecular 2Fe-2As precursor complex was synthesized and transformed under soft reaction conditions to produce an active and long-term stable nanocrystalline FeAs material for electrocatalytic water oxidation in alkaline media. The 2Fe2As-centred ß-diketiminato complex, having an unusual planar Fe2As2 core structure, results from the salt-metathesis reaction of the corresponding ß-diketiminato FeIICl complex and the AsCO- (arsaethynolate) anion as the monoanionic As- source. The as-prepared FeAs phase produced from the precursor has been electrophoretically deposited on conductive electrode substrates and shown to act as a electro(pre)catalyst for the oxygen evolution reaction (OER). The deposited FeAs undergoes corrosion under the severe anodic alkaline conditions which causes extensive dissolution of As into the electrolyte forming finally an active two-line ferrihydrite phase (Fe2O3(H2O) x ). Importantly, the dissolved As in the electrolyte can be fully recaptured (electro-deposited) at the counter electrode making the complete process eco-conscious. The results represent a new and facile entry to unexplored nanostructured transition-metal arsenides and their utilization for high-performance OER electrocatalysis, which are also known to be magnificent high-temperature superconductors.

Individual invitation letters lead to significant increase in attendance for screening colonoscopies: Results of a pilot study in Northern Hesse, Germany.

BACKGROUND: Colorectal cancer (CRC) is the second most common cancer in Germany. Screening colonoscopies are considered an effective tool for early detection and prevention of CRC and are recommended in Germany for citizens over the age of 55. To increase the participation rate for screening colonoscopies, an invitation procedure was initiated in parts of Germany for patients between the ages of 55 and 75 who had never undergone a screening colonoscopy before. METHODS: We examined the number of participating patients before, during, and after the invitation procedure and compared the number of the participating patients who received a cover letter with the participating patients from the control group. Additionally, we classified the findings of the colonoscopies including CRC, advanced adenomas, and polyps. RESULTS: During the invitation period, the participation rate of the invitation group increased from 220 patients to 531 patients compared to 1256 to 1693 in the control group. The increase was significantly greater in patients with cover letters (+141% vs.+35%, p < 0.0001). Also, significantly more polyps and adenomas were found in patients from the invitation letter group (254 (+102%) vs. 679 (-9%), p < 0.0001). CONCLUSIONS: Our study clearly indicates that personal invitation letters are an effective measure to increase overall participation rates in screening colonoscopies.

Altered ratio of collagen chains in bone of a patient with non-lethal osteogenesis imperfecta.

Bone from a patient with osteogenesis imperfecta contained type III collagen which was absent in control bone. The ratio of alpha 1(I)/alpha 2(I) in type I collagen of patient's bone was increased (2.9 vs. 2.3 +/- 0.2 in controls) and the ratio of dimers beta 11/beta 12/beta 22 was altered due to the increased beta 22 content. No abnormality was observed in collagen from the patient's skin. The altered composition of collagen in bone, but the normal composition in skin suggests that the disease in the patient is due to impaired regulation of the synthesis of collagens in bone, rather than by a mutation in one of the two type I collagen genes. Unlike in skin, all the type III collagen in patient's bone was pepsin-soluble indicating an inability of the bone to incorporate type III collagen into mature highly cross-linked extracellular matrix.

Subspectacular nematodiasis caused by a novel Serpentirhabdias species in ball pythons (Python regius).

Subspectacular nematodiasis was diagnosed in three captive-bred juvenile ball pythons (Python regius) from two unrelated facilities within a 6-month period. The snakes were presented with similar lesions, including swelling of facial, periocular and oral tissues. Bilaterally, the subspectacular spaces were distended and filled with an opaque fluid, which contained nematodes and eggs. Histopathology showed nematodes throughout the periocular tissue, subspectacular space and subcutaneous tissue of the head. The nematodes from both facilities were morphologically indistinguishable and most closely resembled Serpentirhabdias species. Morphological characterization and genetic sequencing indicate this is a previously undescribed rhabdiasid nematode.

The effect of low protein-high dextrin diet and subsequent food restriction upon life prolongation in Fischer 344 male rats.

Fischer 344 rats fed low protein-high dextrin diet exhibit a higher median (but not 10th percentile) survival as compared to controls. The effect of this diet appears already if the diet is administered between 6 weeks and 6 months of age; after this treatment median survival of experimental animals is increased by 96 days while the 10th percentile is not different from standard diet-fed controls. Further treatment of animals with the same diet has minimum effect as animals that lived on this regimen throughout the whole life exhibited a median lifespan increase by 120 days and increase in the 10th percentile by 41 days. However, if such animals at the age of 6 months are transferred to a restricted (60%) food intake regimen (control diet, not carbohydrate enriched) a further increase in median and 10th percentile lifespan prolongation can be observed reaching +328 and +396 days respectively as compared to controls. The effects of this early feeding (6 weeks to 6 months) with a low protein-high carbohydrate diet available ad libitum and the food restricted regimen (standard diet 60% controls) fed from the age 6 months onwards are additive, the final results being identical to those obtained if the animals were kept on the 60% food restricted intake throughout the whole life. The fact that animals fed the low protein-high carbohydrate diet and those kept on 60% standard diet food restriction had different survival though they were equal in daily (identical) protein intake is emphasized.

Increased glycation and pigmentation of collagen in aged and young parabiotic rats and mice.

Changes of non-enzymatic collagen glycosylation were followed in 2- and 24-month-old rats and mice and in parabiotic animals of the same age. With advancing age increased glycation of collagen was observed in both old male Wistar rats and white mice. Further it was demonstrated that both aortal and skin collagen of young animals is rapidly non-enzymatically glycosylated in the common milieu created by parabiotic animals and the proportion of non-enzymatically incorporated glucose approaches in the young counterparts the level found in old individuals. Similar trends as with non-enzymatic glycosylation were found with a fluorescent (370/440 nm) product present in both categories of collagen preparations. This fluorescence was higher in old animals and was considerably increased in the young counterpart of the parabiotic couple 6 weeks after operation. The nature of the fluorescent product appears different from pyridinoline and remains to be elucidated.