Enhancing oxygen evolution reactions in nanoporous high-entropy catalysts using boron and phosphorus additives.

High-entropy alloy (HEA) catalysts are a novel area of research in catalysis that shows great potential for more efficient catalyst development. Recent studies have highlighted the promise of HEA catalysts in applications such as water-splitting electrodes, owing to their better stability and ability to improve catalytic activity compared to traditional catalysts. Dealloying, which is a process that removes elements from metallic alloys, is a popular method for creating nanoporous HEA catalysts with large surface areas and interconnected structures. This study focused on the fabrication of nanoporous HEA catalysts with boron and phosphorus additives for the oxygen evolution reaction (OER) in water splitting. Combining B or P with noble metals such as Ir or Ru enhances the OER activity and durability, showing synergistic interactions between metals and light elements. This study used electrochemical evaluations to determine the best-performing catalyst, identifying CoCuFeMoNiIrB as the best catalyst for OERs in alkaline media. X-ray photoemission spectroscopy (XPS) analysis revealed that B effectively shifted the transition elements to higher valence states and induced excess electrons on the Ir-B surface to promote OER catalysis.

All-Solid-State Mg-Air Battery Enhanced with Free-Standing N-Doped 3D Nanoporous Graphene.

Nitrogen (N) doping of graphene with a three-dimensional (3D) porous structure, high flexibility, and low cost exhibits potential for developing metal-air batteries to power electric/electronic devices. The optimization of N-doping into graphene and the design of interconnected and monolithic graphene-based 3D porous structures are crucial for mass/ion diffusion and the final oxygen reduction reaction (ORR)/battery performance. Aqueous-type and all-solid-state primary Mg-air batteries using N-doped nanoporous graphene as air cathodes are assembled. N-doped nanoporous graphene with 50-150 nm pores and ≈99% porosity is found to exhibit a Pt-comparable ORR performance, along with satisfactory durability in both neutral and alkaline media. Remarkably, the all-solid-state battery exhibits a peak power density of 72.1 mW cm-2 ; this value is higher than that of a battery using Pt/carbon cathodes (54.3 mW cm-2 ) owing to the enhanced catalytic activity induced by N-doping and rapid air breathing in the 3D porous structure. Additionally, the all-solid-state battery demonstrates better performances than the aqueous-type battery owing to slow corrosion of the Mg anode by solid electrolytes. This study sheds light on the design of free-standing and catalytically active 3D nanoporous graphene that enhances the performance of both Mg-air batteries and various carbon-neutral-technologies using neutral electrolytes.

Suppression of Methanol and Formate Crossover through Sulfanilic-Functionalized Holey Graphene as Proton Exchange Membranes.

Proton exchange membranes with high proton conductivity and low crossover of fuel molecules are required to realize advanced fuel-cell technology. The selective transportation of protons, which occurs by blocking the transportation of fuel molecules across a proton exchange membrane, is crucial to suppress crossover while maintaining a high proton conductivity. In this study, a simple yet powerful method is proposed for optimizing the crossover-conductivity relationship by pasting sulfanilic-functionalized holey graphenes onto a Nafion membrane. The results show that the sulfanilic-functionalized holey graphenes supported by the membrane suppresses the crossover by 89% in methanol and 80% in formate compared with that in the self-assembled Nafion membrane; an ≈60% reduction is observed in the proton conductivity. This method exhibits the potential for application in advanced fuel cells that use methanol and formic acid as chemical fuels to achieve high energy efficiency.

1T/1H-SnS2 Sheets for Electrochemical CO2 Reduction to Formate.

Understanding the catalytic mechanism of highly active two-dimensional electrocatalysts is crucial to their rational design. Herein, we reveal the element dependence of the reactivity of two-dimensional metal dichalcogenide sheets for electrocatalytic CO2 reduction. We found that tin(IV) disulfide (SnS2) and molybdenum(IV) disulfide (MoS2) sheets exhibited Faradaic efficiencies of 63.3% and ∼0%, respectively, for formic acid. Scanning electrochemical cell microscopy and theoretical calculations were used to identify the catalytically active sites of SnS2 as terraces and edges. Owing to the effective utilization of the entire surface area, SnS2 can effectively accelerate catalytic reactions. This finding provides a direction for material research in two-dimensional electrocatalysts for energy-efficient chemical production from electrochemical CO2 reduction, as well as for other energy devices.

Crovalimab treatment in patients with paroxysmal nocturnal haemoglobinuria: Long-term results from the phase I/II COMPOSER trial.

OBJECTIVES: This study reports long-term outcomes from the open-label extension (OLE) period of the Phase I/II COMPOSER trial (NCT03157635) that evaluated crovalimab in patients with paroxysmal nocturnal haemoglobinuria, who were treatment-naive or switched from eculizumab at enrolment. METHODS: COMPOSER consists of four sequential parts followed by the OLE. The primary OLE objective was to assess long-term crovalimab safety, with a secondary objective to assess crovalimab pharmacokinetics and pharmacodynamics. Exploratory efficacy endpoints included change in lactate dehydrogenase (LDH), transfusion avoidance, haemoglobin stabilisation and breakthrough haemolysis (BTH). RESULTS: A total 43 of 44 patients entered the OLE after completing the primary treatment period. Overall, 14 of 44 (32%) experienced treatment-related adverse events. Steady state exposure levels of crovalimab and terminal complement inhibition were maintained over the OLE. During the OLE, mean normalised LDH was generally maintained at ≤1.5× upper limit of normal, transfusion avoidance was achieved in 83%-92% of patients and haemoglobin stabilisation was reached in 79%-88% of patients across each 24-week interval. Five BTH events occurred with none leading to withdrawal. CONCLUSIONS: Over a 3-year median treatment duration, crovalimab was well tolerated and sustained C5 inhibition was achieved. Intravascular haemolysis control, haemoglobin stabilisation and transfusion avoidance were maintained, signifying long-term crovalimab efficacy.

Mitigating Drug-Target-Drug Complexes in Patients With Paroxysmal Nocturnal Hemoglobinuria Who Switch C5 Inhibitors.

Drug-target-drug complexes (DTDCs) are phenomena newly observed in patients who switch from the complement component 5 (C5) inhibitor eculizumab to crovalimab, a novel, anti-C5 antibody in development for paroxysmal nocturnal hemoglobinuria (PNH), because these agents bind to different C5 epitopes. In Part 3 of the four-part, phase I/II COMPOSER study, 19 patients with PNH switching from eculizumab received 1,000-mg crovalimab intravenously, then subcutaneous maintenance doses from Day 8 (680 mg every 4 weeks (q4w), 340 mg every 2 weeks, or 170 mg every week). Crovalimab exposure was transiently reduced, and size-exclusion chromatography and crovalimab-specific enzyme-linked immunosorbent assays revealed DTDCs in all 19 patients' sera. Additionally, self-limiting mild to moderate symptoms suggestive of type III hypersensitivity reactions occurred in two patients. Mathematical modeling simulations of DTDC kinetics and effects of dosing on DTDC size distribution using Part 3 data predicted that increased crovalimab concentrations could reduce the proportion of large, slow-clearing DTDCs in the blood. A simulation-guided, optimized crovalimab regimen (1,000 mg intravenously; four weekly, subcutaneous 340-mg doses; then 680 mg q4w from Day 29) was evaluated in Part 4. Confirming the model's predictions, mean proportions of large DTDCs in patients who switched from eculizumab to this optimized regimen decreased by > 50% by Day 22, and target crovalimab concentrations were maintained. No type III hypersensitivity reactions occurred in Part 4. Optimizing crovalimab dosing thus reduced the proportion of large DTDCs, ensured adequate complement inhibition, and may improve safety. Model-based dosing optimization to mitigate DTDC formation offers a useful strategy for patients switching to novel antibody treatments targeting soluble epitopes.

Corrosion-Resistant and High-Entropic Non-Noble-Metal Electrodes for Oxygen Evolution in Acidic Media.

To realize a sustainable hydrogen economy, corrosion-resistant non-noble-metal catalysts are needed to replace noble-metal-based catalysts. The combination of passivation elements and catalytically active elements is crucial for simultaneously achieving high corrosion resistance and high catalytic activity. Herein, the self-selection/reconstruction characteristics of multi-element (nonary) alloys that can automatically redistribute suitable elements and rearrange surface structures under the target reaction conditions during the oxygen evolution reaction are investigated. The following synergetic effect (i.e., cocktail effect), among the elements Ti, Zr, Nb, and Mo, significantly contributes to passivation, whereas Cr, Co, Ni, Mn, and Fe enhance the catalytic activity. According to the practical water electrolysis experiments, the self-selected/reconstructed multi-element alloy demonstrates high performance under a similar condition with proton exchange membrane (PEM)-type water electrolysis without obvious degradation during stability tests. This verifies the resistance of the alloy to corrosion when used as an electrode under a practical PEM electrolysis condition.

Tuning the Electronic Response of Metallic Graphene by Potassium Doping.

Electron doping of graphene has been extensively studied on graphene-supported surfaces, where the metallicity is influenced by the substrate. Herewith we propose potassium adsorption on free-standing nanoporous graphene, thus eluding any effect due to the substrate. We monitor the electron migration in the π* downward-shifted conduction band. In this rigid band shift, we correlate the spectral density of the π* state in the upper Dirac cone with the associated plasmon, blue-shifted with increasing K dose, as deduced by electron energy loss spectroscopy. These results are confirmed by the Dirac plasmon activated by the C 1s emitted electrons, thanks to spatially resolved photoemission. This crosscheck constitutes a reference on the correlation between the electronic π* states in the conduction band and the Dirac plasmon evolution upon in situ electron doping of fully free-standing graphene.

General Synthesis of MOF Nanotubes via Hydrogen-Bonded Organic Frameworks toward Efficient Hydrogen Evolution Electrocatalysts.

The application scope of metal-organic frameworks (MOFs) can be extended by rationally designing the architecture and components of MOFs, which can be achieved via a metal-containing solid templated strategy. However, this strategy suffers from low efficiency and provides only one specific MOF from one template. Herein, we present a versatile templated strategy in which organic ligands are weaved into hydrogen-bonded organic frameworks (HOFs) for the controllable and scalable synthesis of MOF nanotubes. HOF nanowires assembled from benzene-1,3,5-tricarboxylic acid and melamine via a simple sonochemical approach serve as both the template and precursor to produce MOF nanotubes with varied metal compositions. Hybrid nanotubes containing nanometal crystals and N-doped graphene prepared through a carbonization process show that the optimized NiRuIr alloy@NG nanotube exhibits excellent electrocatalytic HER activity and durability in alkaline media, outperforming most reported catalysts. The strategy proposed here demonstrates a pioneering study of combination of HOF and MOF, which shows great potential in the design of other nanosized MOFs with various architectures and compositions for potential applications.

Coexistence of Urbach-Tail-Like Localized States and Metallic Conduction Channels in Nitrogen-Doped 3D Curved Graphene.

Nitrogen (N) doping is one of the most effective approaches to tailor the chemical and physical properties of graphene. By the interplay between N dopants and 3D curvature of graphene lattices, N-doped 3D graphene displays superior performance in electrocatalysis and solar-energy harvesting for energy and environmental applications. However, the electrical transport properties and the electronic states, which are the key factors to understand the origins of the N-doping effect in 3D graphene, are still missing. The electronic properties of N-doped 3D graphene are systematically investigated by an electric-double-layer transistor method. It is demonstrated that Urbach-tail-like localized states are located around the neutral point of N-doped 3D graphene with the background metallic transport channels. The dual nature of electronic states, generated by the synergistic effect of N dopants and 3D curvature of graphene, can be the electronic origin of the high electrocatalysis, enhanced molecular adsorption, and light absorption of N-doped 3D graphene.

Tyrosine Kinase Inhibitors Do Not Promote a Decrease in SARS-CoV-2 Anti-Spike IgG after BNT162b2 Vaccination in Chronic Myeloid Leukemia: A Prospective Observational Study.

We performed a prospective observational study of chronic myeloid leukemia (CML) patients after anti-SARS-CoV-2 BNT162b2 vaccination (VC). In total, 32 CML patients with tyrosine kinase inhibitor (TKI) therapy, 10 CML patients with treatment-free remission, and 16 healthy subjects participated in the study. From April 2021 to September 2021, all cases (median age = 58 years) were vaccinated twice. Immunoglobulin G for SARS-CoV-2 spike protein (S-IgG) was measured at three timepoints (before the first VC, 1−5 weeks after the second VC (T1), and approximately 6 months after the second VC (T2)). S-IgG was not observed before the first VC in any participant. At T1, all cases had acquired S-IgG. There were no significant differences in S-IgG levels among groups. A paired sample comparison of median S-IgG titers between T1 and T2 in all groups showed a significant reduction in T2 S-IgG titers. There were no significant differences in S-IgG levels among groups. When all patients were analyzed, those aged ≥58 years had significantly lower S-IgG levels than those aged <58 years at T1. The BNT162b2 vaccine was highly effective in CML patients with or without TKIs, and S-IgG levels were as persistent as those in healthy individuals.

Homogeneous Spatial Distribution of Deuterium Chemisorbed on Free-Standing Graphene.

Atomic deuterium (D) adsorption on free-standing nanoporous graphene obtained by ultra-high vacuum D2 molecular cracking reveals a homogeneous distribution all over the nanoporous graphene sample, as deduced by ultra-high vacuum Raman spectroscopy combined with core-level photoemission spectroscopy. Raman microscopy unveils the presence of bonding distortion, from the signal associated to the planar sp2 configuration of graphene toward the sp3 tetrahedral structure of graphane. The establishment of D-C sp3 hybrid bonds is also clearly determined by high-resolution X-ray photoelectron spectroscopy and spatially correlated to the Auger spectroscopy signal. This work shows that the low-energy molecular cracking of D2 in an ultra-high vacuum is an efficient strategy for obtaining high-quality semiconducting graphane with homogeneous uptake of deuterium atoms, as confirmed by this combined optical and electronic spectro-microscopy study wholly carried out in ultra-high vacuum conditions.

Prospective comparison of 5- and 7-day administration of azacitidine for myelodysplastic syndromes: a JALSG MDS212 trial.

The hypomethylating agent azacitidine (AZA) significantly extends overall survival (OS) in patients with higher risk myelodysplastic syndromes (MDS), when compared with other conventional care regimens, including supportive care and low-dose and intensive chemotherapy. However, the effects of 5- and 7-day treatment schedules of AZA (AZA-5 and AZA-7, respectively) on the OS of MDS patients had not been compared prospectively. We started a phase 3 trial comparing the effects of AZA-7 and AZA-5 on MDS patients with refractory anemia with excess blasts (RAEB) and RAEB in transformation (RAEB-T). However, this trial was prematurely terminated because of poor recruitment. Using all data, there was no significant difference in the OS of patients between AZA-7 (92 patients) and AZA-5 (95 patients), with the 2-year OS rates of AZA-7 and AZA-5 at 36.4% and 25.8%, respectively (P = 0.293). Adverse event profiles were similar between the two groups. Interestingly, data of the centrally diagnosed RAEB and RAEB-T cases showed that AZA-7 significantly prolonged the time to leukemia transformation compared with AZA-5 (P = 0.022), confirmed by multivariate analysis. Although this trial could not provide definite evidence, the results support the use of AZA-7 for RAEB and RAEB-T. (UMIN Clinical Trials Registry UMIN000009633).

Gap Opening in Double-Sided Highly Hydrogenated Free-Standing Graphene.

Conversion of free-standing graphene into pure graphane─where each C atom is sp3 bound to a hydrogen atom─has not been achieved so far, in spite of numerous experimental attempts. Here, we obtain an unprecedented level of hydrogenation (≈90% of sp3 bonds) by exposing fully free-standing nanoporous samples─constituted by a single to a few veils of smoothly rippled graphene─to atomic hydrogen in ultrahigh vacuum. Such a controlled hydrogenation of high-quality and high-specific-area samples converts the original conductive graphene into a wide gap semiconductor, with the valence band maximum (VBM) ∼ 3.5 eV below the Fermi level, as monitored by photoemission spectromicroscopy and confirmed by theoretical predictions. In fact, the calculated band structure unequivocally identifies the achievement of a stable, double-sided fully hydrogenated configuration, with gap opening and no trace of π states, in excellent agreement with the experimental results.

Collection of 2429 constrained headshots of 277 volunteers for deep learning.

Deep learning has rapidly been filtrating many aspects of human lives. In particular, image recognition by convolutional neural networks has inspired numerous studies in this area. Hardware and software technologies as well as large quantities of data have contributed to the drastic development of the field. However, the application of deep learning is often hindered by the need for big data and the laborious manual annotation thereof. To experience deep learning using the data compiled by us, we collected 2429 constrained headshot images of 277 volunteers. The collection of face photographs is challenging in terms of protecting personal information; we therefore established an online procedure in which both the informed consent and image data could be obtained. We did not collect personal information, but issued agreement numbers to deal with withdrawal requests. Gender and smile labels were manually and subjectively annotated only from the appearances, and final labels were determined by majority among our team members. Rotated, trimmed, resolution-reduced, decolorized, and matrix-formed data were allowed to be publicly released. Moreover, simplified feature vectors for data sciences were released. We performed gender and smile recognition by building convolutional neural networks based on the Inception V3 model with pre-trained ImageNet data to demonstrate the usefulness of our dataset.

Ocular infestation by a juvenile leech, Myxobdella sinanensis in Japan.

PURPOSE: The case of ocular infestation by a leech is rare. We reported that Myxobdella sinanensis infests conjunctiva. OBSERVATIONS: A 5-year-old girl presented with blood clots in the inner corner of the left eye, and a history bloody eye discharge and bloody tears for 5 days. She was prescribed 0.5% levofloxacin ophthalmic drops for conjunctival damage. However, her parent watched a worm moving in her conjunctiva while taking a bath. She presented again the same day, and a worm was found in the left eye of the lower conjunctival fornix and was adsorbed to the inner corner. We removed a worm under eye drop anesthesia, the next day the patient had no symptoms. We captured the worm, and it was identified morphologically and genetically as Myxobdella sinanensis. This was the first case reported of Myxobdella sinanensis be infestation in a human. CONCLUSIONS AND IMPORTANCE: The ecological trait of Myxobdella sinanensis still did not remain clear, so this case report was helpful to find out a life cycle of Myxobdella sinanensis. As the outdoor population continues to increase, the cases of human parasites such as leech are expected to increase. When a patient with bloody eye discharge and bloody tears presents, we should carefully examine the conjunctiva and ocular surfaces, and interview recent history of exposure to stream water.

A phase II randomized study evaluating azacitidine versus conventional care regimens in newly diagnosed elderly Japanese patients with unfavorable acute myeloid leukemia.

A multicenter phase II study was conducted in 44 elderly (≥ 65 years) Japanese patients with newly diagnosed acute myeloid leukemia (AML) to evaluate whether azacitidine is also effective and feasible in Japanese AML patients. The 28 patients with AML with poor-risk cytogenetics and/or myelodysplasia-related changes (unfavorable AML) were randomly assigned to receive either azacitidine or conventional care regimens (CCR), and the other 16 patients without unfavorable AML received azacitidine alone. The primary endpoint was overall survival. At the median follow-up of 29 months, among the 26 evaluable patients with unfavorable AML, the median survival time (MST) of patients who received azacitidine (N = 14) was 9.6 months and that of patients who received CCR (N = 12) was 5.3 months (HR 0.73; 95% CI 0.31-1.69; log-rank P = 0.459). The MST of all 29 patients who received azacytidine, including the 15 evaluable patients without unfavorable AML, was 12.4 months. Adverse events of azacitidine were manageable and consistent with its established safety profile. Azacitidine tended to prolong survival in newly diagnosed elderly Japanese patients with AML, and was feasible as a front-line therapy for elderly AML patients.

Retinal Nerve Fiber Layer Thickness and Rim Area Profiles in Asians: Pooled Analysis from the Asian Eye Epidemiology Consortium.

PURPOSE: To evaluate ethnic variations, ocular and systemic determinants of retinal nerve fiber layer (RNFL) thickness, and neuroretinal rim area among Asians using a large consortium of population-based eye studies. DESIGN: Cross-sectional pooled analysis. PARTICIPANTS: Twenty-two thousand four hundred thirty-six participants (22 436 eyes) from 10 population-based studies (in China, Hong Kong, India, Japan, Russia, and Singapore) of the Asian Eye Epidemiology Consortium. METHODS: Participants 40 years of age or older without glaucoma were included. All participants underwent spectral-domain OCT imaging and systemic and ocular examinations. Data were pooled from each study. Multivariable regression was performed to evaluate interethnic differences, intermachine variations, and ocular and systemic factors associated with RNFL thickness and rim area, adjusting for age, gender, diabetes, intraocular pressure (IOP), spherical equivalent (SE), ethnicity, OCT model, and study group. When evaluating body mass index, smoking, and hypertension as exposures, these factors were additionally adjusted for in the model. MAIN OUTCOME MEASURES: Average RNFL thickness (in micrometers) and rim area (in square millimeters). RESULTS: Indian and Japanese eyes have thinner RNFLs than those of other Asian ethnicities (ß values range, 7.31-12.76 µm; P < 0.001 for all pairwise comparisons). Compared with measurements by Cirrus HD-OCT (Carl Zeiss Meditec, Inc), RNFL on average was 7.29 µm thicker when measured by Spectralis (Heidelberg Engineering), 12.85 µm thicker when measured by RS-3000 (NIDEK Co, Ltd), and 17.48 µm thicker when measured by iVue/RTVue (Optovue, Inc) devices (all P < 0.001). Additionally, older age (per decade, ß = -2.70), diabetes (ß = -0.72), higher IOP (per 1 mmHg, ß = -0.07), more myopic SE (per diopter, ß = -1.13), cardiovascular disease (ß = -0.94), and hypertension (ß = -0.68) were associated with thinner RNFL (all P ≤ 0.003). Similarly, older age (ß = -0.019), higher IOP (ß = -0.010), and more myopic SE (ß = -0.025) were associated with smaller rim area (all P < 0.001). CONCLUSIONS: In this large pooled analysis of Asian population studies, Indian and Japanese eyes were observed to have thinner RNFL profiles. These findings suggest the need for an ethnic-specific normative database to improve glaucoma detection.

Nanoporous ultra-high-entropy alloys containing fourteen elements for water splitting electrocatalysis.

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity via dealloying. These np-UHEAs contain up to 14 elements, namely, Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti. Furthermore, they exhibit high catalytic activities and electrochemical stabilities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic media, superior to that of commercial Pt/graphene and IrO2 catalysts. Our results offer valuable insights for the selection of elements as catalysts for various applications.