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Specifically, the high-entropy composite exhibits an OER activity comparable to the best reported value, and the ORR activity exceeded the performance of commercial Pt/C in alkaline solutions with a record-low bifunctional ΔE of 0.61 V in 0.1 M KOH solution. This work shows an important route to prepare complex HEA@HEO nanocomposites with tuned catalytic performance for multifunctional catalysis and energy conversion.Considering nearly infinite design possibilities, organic second harmonic generation (SHG) molecules are believed to have long-term promise. However, because of the tendency to form dipole-antiparallel crystals that lead to zero macroscopic polarization, it is difficult to design a nonlinear optical (NLO) material based on organic molecules. In this manuscript, we report a new molecule motif that can form asymmetric organic solids by controlling the degree of hydrogen bonding through protonation. A conjugated polar organic molecule was prepared with a triple bond connecting an electron-withdrawing pyridine ring and an electron-donating thiophene ring. By controlling the degree of hydrogen bonding through protonation, two different crystal packing motifs are achieved. One crystallizes into the common dipole-antiparallel nonpolar P1̄ space group. The second crystallizes into the uncommon dipole-parallel polar P1 space group, in which the molecular dipoles are aligned along a single axis and thus exhibit a high macroscopic polarization in its solid-state form. Due to the P1 polar packing, the sample can generate second harmonic light efficiently, about three times the intensity of the benchmark potassium dihydrogen phosphate. Our findings show that crystal engineering by hydrogen bonding in a single molecular backbone can be used for controlling the macroscopic NLO properties.Biosensors and bioassays, both of which employ proteins and nucleic acids to detect specific molecular targets, have seen significant applications in both biomedical research and clinical practice. This success is largely due to the extraordinary versatility, affinity, and specificity of biomolecular recognition. Nevertheless, these receptors suffer from an inherent limitation single, saturable binding sites exhibit a hyperbolic relationship (the "Langmuir isotherm") between target concentration and receptor occupancy, which in turn limits the sensitivity of these technologies to small variations in target concentration. To overcome this and generate more responsive biosensors and bioassays, here we have used the sequestration mechanism to improve the steepness of the input/output curves of several bioanalytical methods. As our test bed for this we employed sensors and assays against neutrophil gelatinase-associated lipocalin (NGAL), a kidney biomarker for which enhanced sensitivity will improve the monitoring of kidney injury. Specifically, by introducing sequestration we have improved the responsiveness of an electrochemical aptamer based (EAB) biosensor, and two bioassays, a paper-based "dipstick" assay and an enzyme-linked immunosorbent assay (ELISA). Doing so we have narrowed the dynamic range of these sensors and assays several-fold, thus enhancing their ability to measure small changes in target concentration. Given that introducing sequestration requires only the addition of the appropriate concentration of a high-affinity "depletant," the mechanism appears simple and easily adaptable to tuning the binding properties of the receptors employed in a wide range of biosensors and bioassays.Mixed-matrix membranes (MMMs) provide a means to formulate metal-organic frameworks (MOFs) into processable films that can help to advance their use in various applications. Conventional MMMs are inherently susceptible to craze or tear upon exposure to impact, cutting, bending, or stretching, which can limit their intended service life and usage. Herein, a simple, efficient, and scalable in situ fabrication approach was used to prepare self-healing MMMs containing Zr(iv)-based MOFs. The ability of these MMMs to self-heal at room temperature is based on the reversible hydrolysis of boronic-ester conjugates. Thiol-ene 'photo-click' polymerization yielded robust MMMs with ∼30 wt% MOF loading and mechanical strength that varied based on the size of MOF particles. The MMMs could undergo repeated self-healing with good retention of mechanical strength. In addition, the MMMs were catalytically active toward the degradation of the chemical warfare agent (CWA) simulant dimethyl-4-nitrophenyl phosphate (DMNP) with no change in activity after two damage-healing cycles.Procedures for the reductive coupling of carbonyl compounds to alkenes in the literature rely either on a radical coupling strategy, as in the McMurry coupling, or ionic pathways, sometimes catalysed by transition metals, as in more contemporary contributions. Herein, we present the first example of a third strategy that is based on the [2 + 2] cycloaddition of ketone-derived phosphaalkenes. Removal of P-trimethylsilyl groups at the intermediary 1,2-diphosphetane dimer results in its collapse and concomitant release of the tetraaryl-substituted alkene. In fact, the presented strategy is the only alternative to the McMurry coupling in the literature that allows tetraaryl alkene formation from diaryl ketones, with yields as high as 85%. The power of the methodology is illustrated in the reaction of tethered bis-benzophenones which engage in intramolecular reductive carbonyl couplings to form unusual macrocycles without the need for high dilution conditions or templating.Inducing the surface enrichment of active noble metal can not only help to stabilize the catalyst but also modify the catalytic performance of the catalyst through electronic and geometric effects. CX-5461 price Herein, we report the in situ surface enrichment of Ir on IrRu alloy during the oxygen evolution reaction (OER). The surface enrichment of Ir was probed by ex situ high-resolution transmission electron microscopy (HRTEM), in situ X-ray absorption spectroscopy (XAS), and electrochemical Cu stripping, leading to complementary characterizations of the dynamic reconstruction of the IrRu alloy during OER. Guided by the density functional theory (DFT), an IrRu alloy with low Ir content (20 wt%) was constructed, which displayed a low overpotential of only 230 mV to deliver an OER current density of 10 mA cm-2 in 0.1 M HClO4 solution and maintained stable performance for over 20 h. To investigate the practical application potential, a proton exchange membrane (PEM) water electrolyzer using the IrRu alloy as the anode catalyst was assembled, which required a low cell voltage of only 1.48 V to generate a current density of 1 A cm-2.The genus Parahubrechtia Gibson and Sundberg, 1999 was first described within the family Hubrechtiidae (class Pilidiophora) and subsequently transferred to the family Callineridae (class Palaeonemertea). Here we describe two new species, Parahubrechtia rayi sp. nov. from the Sea of Japan (Russia) and P. peri sp. nov. from the South China Sea (China). A phylogenetic analysis based on partial sequences of five nuclear and mitochondrial gene regions, 18S rRNA, 28S rRNA, histone H3, 16S rRNA, and COI, has confirmed the monophyly of the genus Parahubrechtia, and indicated a close relationship to Callinera Bergendal, 1900, whose monophyly is not confirmed. Both genera belong to the family Tubulanidae, with its junior synonym being Callineridae. Three major subclades are distinguished within the Tubulanidae subclade Tubulanus s. str., subclade Tubulanus punctatus, and subclade Parahubrechtia + Callinera. The further status of Parahubrechtia depends on whether the paraphyly of Callinera is confirmed or not and how the problem of paraphyly of the genus Tubulanus Renier, 1804 is resolved.Darevskia is a particularly species-rich radiation of Palearctic rock lizards from the Caucasus region. Thanks to intense systematic and taxonomic research, the knowledge of species-level diversity within this genus has increased over the last quarter century. Here, we described a new species, Darevskia salihae sp. nov. from northeastern Turkey. The new taxon is differentiated from other nearby taxon by the low number of dorsal scales in the middle of the body, the shorter body length, and the absence of blue dots both on the lateral region above the forelimbs and on the margin of the ventral plates. In addition to their morphological differences, the new taxon is phylogenetically different from close groups. It is located in a separate subclade from the rudis-valentini-portschinskii subclade. This distinction is supported by both a high bootstrap value (100) and a high posterior probability value (1.00). These two subclades are separated from each other by a genetic distance of almost 4%. This separation is supported not only genetically and morphologically, but also geographically. Since the habitat of the new taxon is limited to a high mountain and a narrow valley, it does not provide an opportunity for a different Darevskia species to shelter because it creates geographical isolation. However, Darevskia parvula that live closest to the habitat of the new taxon live only at the habitat boundaries and do not enter areas where the new taxon is found. Therefore, it might be possible that while it was separated from the rudis-valentini-portschinskii group during the evolutionary transformation, it remained as a refuge and relict in a narrow area as a result of the collapse of the valleys and the partial uplift of the Kaçkar Mountains.Patients with thromboembolic disorders are commonly on anticoagulants; hence, they are susceptible to bleeding episodes such as ecchymosis, gingival, subconjunctival bleeding, and rarely can have intramural hematoma of small bowel causing patient to present with intestinal obstruction. It is a rare cause of mechanical bowel obstruction requiring a nonsurgical management. Our patient was a 55-year-old male, a known case of thromboembolism on warfarin medication, presented with abdominal pain and vomiting. Patient's laboratory reports reflected anemia and deranged coagulation profile with prothrombin time and international normalized ratio, both being elevated. Intramural hematoma of jejunum was diagnosed by abdominal contrast-enhanced computed tomography. Conservative management was done, warfarin was stopped and vitamin K was administered. Patient received fresh frozen plasma and packed cell blood. It is important to suspect warfarin toxicity in patients on the medication who come with such presentation to avoid surgical management, which could be catastrophic due to excessive bleeding. It is important for regular monitoring of coagulation profile of such patients and to reduce prescribing other medications that can interact with warfarin. It is worth noting that novel oral anticoagulants, such as dabigatran and rivaroxaban, are associated with fewer side effects and do not require close laboratory monitoring.Background  Spigelian hernias are a rare type of lateral ventral abdominal hernia and their content can include any of the intra-abdominal organs. Many cases have described the presence of a variety of abdominal organs in Spigelian hernias, but only few cases report the presence of an incarcerated appendicitis. Imaging is an important step in the diagnosis to avoid the lack of knowledge in such cases. Surgical treatment can be through open or laparoscopic approach, with or without using a mesh according to the size of the defect. Case Report  We report a case of an 82-year-old patient who presented with an acute appendicitis with peri-appendicular abscess strangulated in a right Spigelian hernia. The patient was successfully treated by a laparoscopic appendectomy, a surgical drainage of the abscess, and direct muscle approximation without using of mesh due to inflammation. Conclusion  Spigelian hernias with acute appendicitis in their content are a very rare condition. Clinical diagnosis is usually difficult and challenging and computed tomography scan is the imaging modality of choice.