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Objective. Pain after a stroke interferes with daily life and the rehabilitation process. This study aimed to clarify the prognosis of pain in subgroups of patients with pain after a stroke using pain quality data. Methods. The study included 85 patients with pain after stroke undergoing exercise-based rehabilitation. Items of the Neuropathic Pain Symptom Inventory (NPSI) were used, and patients with pain after stroke were clustered according to their scores of NPSI. Other clinical assessments, such as physical and psychological conditions, were assessed by interviews and questionnaires, and then these were compared among subgroups in a cross-sectional analysis. Longitudinal pain intensity in each subgroup was recorded during 12 weeks after the stroke and the patients' pain prognoses were compared between subgroups. Results. Four distinct subgroups were clustered: cluster 1 (cold-evoked pain and tingling), cluster 2 (tingling only), cluster 3 (pressure-evoked pain), and cluster 4 (deep muscle pain with a squeezing and pressure sensation). The cross-sectional analysis showed varying clinical symptoms among the subgroups, with differences in the prevalence of joint pain, limited range of motion, somatosensory dysfunction, and allodynia. There were no significant differences in pain intensity at baseline among the subgroups. A longitudinal analysis showed divergent prognoses of pain intensity among the subgroups. The pain intensity in cluster 4 was significantly alleviated, which suggested that musculoskeletal pain could be reduced with conventional exercise-based rehabilitation. However, the pain intensity of patients in clusters 1 and 2 remained over 12 weeks. Conclusion. The study classified patients into clinically meaningful subgroups using pain quality data and provided insight into their prognosis of pain. The findings could be useful for guiding personalized rehabilitation strategies for pain management. Impact. Assessment of pain quality in patients with pain after stroke leads to personalized rehabilitation for pain management. Keywords: Pain, Subgroups, Post-Stroke Pain, Introduction After a cerebrovascular accident, patients may have several types of pain, such as shoulder pain, muscle spasm-induced pain, and neuropathic pain. Such types of pain are all-inclusively called pain [...]

Despite more women and underrepresented students entering engineering, there are still gaps in achievement. A potential remedy is to establish equitable team dynamics during groupwork. Groupware systems have been implemented in the workforce and, recently, piloted in undergraduate lower-division education to establish team norms. Our prior work found that there was a significant association between gender and the utility of rules systems to establish team norms. To assess biases regarding gender and minority groups in the rules system, we examined the differences between rules chosen by individuals and teams based on demographic characteristics in a large engineering course. Students individually identified which rules were most important when working in a team, then formed teams and performed a 'negotiation' to choose which rules the team would follow. We used-statistical analyses to determine whether certain demographic factors predicted how influential an individual was during the selection process. We found that demographic and educational characteristics did not have a significant influence on decision-making for team rules. Furthermore, we found that female and first-generation students were more likely to select the rule 'Play an active part in the team' than their male or continuing-generation peers., There has been a significant amount of research that highlights issues in engineering education with differential success for different groups of undergraduates (de Cohen & Deterding, 2009; Garrison, 2013; Malicky, [...]

Ultrafast stimuli can stabilize metastable states of matter inaccessible by equilibrium means. Establishing the spatiotemporal link between ultrafast excitation and metastability is crucial to understand these phenomena. Here we utilize single-shot optical pump–X-ray probe measurements to capture snapshots of the emergence of a persistent polar vortex supercrystal in a heterostructure that hosts a fine balance between built-in electrostatic and elastic frustrations by design. By perturbing this balance with photoinduced charges, an initially heterogeneous mixture of polar phase disorders within a few picoseconds, leading to a state composed of disordered ferroelectric and suppressed vortex orders. On the picosecond–nanosecond timescales, transient labyrinthine fluctuations develop, accompanied by the recovery of the vortex order. On longer timescales, these fluctuations are progressively quenched by dynamical strain modulations, which drive the collective emergence of a single vortex supercrystal phase. Our results, corroborated by dynamical phase-field modelling, reveal non-equilibrium pathways following the ultrafast excitation of designer systems to persistent metastability.

There is no established risk score for anticoagulant-related bleeding during the acute phase in patients with pulmonary embolism (PE). The PE-Syncope, Anemia, and Renal Dysfunction (PE-SARD) bleeding score was developed to predict early major bleeding but has not yet been fully externally validated.

Despite clinical implications, the pathogenesis of mucus plugging in asthma, chronic obstructive pulmonary disease (COPD), and asthma-COPD overlap (ACO) remains unclear. We hypothesized that distinct airway microbiomes might affect mucus plugging differently among ACO, asthma, and COPD and among different extents of airway eosinophilic inflammation.

Co-detection of respiratory pathogens with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is poorly understood. This descriptive epidemiological study aimed to determine the effect of the interaction of different respiratory pathogens on clinical variables.

The layer structure of 3C-SiC stacked on 4H-SiC is implemented by simultaneous lateral epitaxy (SLE). The SLE, involving spontaneous nucleation of 3C-SiC(111) on the 4H-SiC(0001) surface followed by step-controlled epitaxy, facilitates the creation of a single-domain 3C-SiC layer with an epitaxial relationship to the underlying 4H-SiC, establishing a coherent (111)//(0001) interface aligned in the basal plane. An extremely low state density at an interface between thermally grown SiO2 and SLE-grown 3C-SiC layer is revealed by local deep level transient spectroscopy (local-DLTS) based on scanning nonlinear dielectric microscopy (SNDM).

In this study, the simultaneous realization of high-speed and high-temperature switching operations is demonstrated using a custom-made high-speed and high-temperature power module installed with a silicon carbide (SiC) CMOS gate driver, which can reduce gate loop inductance and operate at high temperatures. Approximate switching speeds of 70 and 60 V/ns are achieved during the turn-on and turn-off operations, respectively, at 300°C, 600 V DC bus voltage, and 20 A load current using the developed module. The switching speed remained above 50 V/ns in the temperature range from room temperature to 300°C. Numerical calculations based on the static properties of the SiC power MOSFET and CMOS gate driver can predict the actual switching properties over a wide temperature range when the developed module incorporating the fabricated SiC CMOS gate driver is used.

Chiral molecular assemblies have attracted considerable attention because of their interesting physical properties, such as spin-selective electron transport. Cation–anion salts of three azolium cations, imidazolium (HIm+), triazolium (HTrz+), and thiazolium (HThz+), in combination with a chiral camphorsulfonate (1S-CS–) and their racemic compounds (rac-CS–) were prepared and compared in terms of phase transitions, crystal structures, dynamics of constituent molecules, dielectric responses, and proton conductivities. The cation–anion crystals containing HIm+showed no significant difference in proton conductivity between the homochiral and racemic crystals, whereas the HTrz+-containing crystals showed higher proton conductivity and lower activation energy in the homochiral form than in the racemic form. A two-dimensional hydrogen-bonding network consisting of HTrz+and −SO3–groups and similar in-plane rotational motion was observed in both crystals; however, the HTrz+cation in the homochiral crystal exhibited the rotational motion modulated with translational motion, whereas the HTrz+cation in the racemic crystal exhibited almost steady in-plane rotational motion. The different motional degrees of freedom were confirmed by crystal structure analyses and temperature- and frequency-dependent dielectric constants. In contrast, steady in-plane rotational motion with the thermally activated fluctuating motion of CS–was observed both in homochiral and racemic crystals containing HIm+, which averaged the motional space of protons resulting in similar dielectric responses and proton conductivities. The control of motional degrees of freedom in homochiral crystals affects the proton conductivity and is useful for the design of molecular proton conductors.

Changes in the gut microbiome have pivotal roles in the pathogenesis of acute graft-versus-host disease (aGVHD) after allogenic haematopoietic cell transplantation (allo-HCT)1–6. However, effective methods for safely resolving gut dysbiosis have not yet been established. An expansion of the pathogen Enterococcus faecalisin the intestine, associated with dysbiosis, has been shown to be a risk factor for aGVHD7–10. Here we analyse the intestinal microbiome of patients with allo-HCT, and find that E. faecalisescapes elimination and proliferates in the intestine by forming biofilms, rather than by acquiring drug-resistance genes. We isolated cytolysin-positive highly pathogenic E. faecalisfrom faecal samples and identified an anti-E. faecalisenzyme derived from E. faecalis-specific bacteriophages by analysing bacterial whole-genome sequencing data. The antibacterial enzyme had lytic activity against the biofilm of E. faecalisin vitro and in vivo. Furthermore, in aGVHD-induced gnotobiotic mice that were colonized with E. faecalisor with patient faecal samples characterized by the domination of Enterococcus, levels of intestinal cytolysin-positive E.faecaliswere decreased and survival was significantly increased in the group that was treated with the E. faecalis-specific enzyme, compared with controls. Thus, administration of a phage-derived antibacterial enzyme that is specific to biofilm-forming pathogenic E. faecalis—which is difficult to eliminate with existing antibiotics—might provide an approach to protect against aGVHD.

Synthesis of the A/D/E-ring core compounds of maoecrystal V was achieved. The key Diels-Alder reactions between tricyclic α-methylene lactones and Kitahara-Danishefsky dienes afforded the spirocyclic core compounds in a regioselective and stereoselective manner.Graphical AbstractSynthesis of the A/D/E-ring core compounds of maoecrystal V was achieved using Diels-Alder reactions between α-methylene lactones and Kitahara-Danishefsky dienes.

DOATS score and DOAT score, COVID-19 progression prediction tools we have developed, utilize clinical information such as presence of diabetes/obesity (DO), age (A), body temperature (T), and oxygen saturation (S). They showed good predictive power, but their scoring calculation was slightly complex, leading us to develop simplified versions. This report discusses the ability of the simplified versions to assess deterioration risk in unvaccinated, mild/moderate COVID-19 patients aged <65 years. Logistic regression analysis identified independent risk factors for deterioration, to which points were assigned in order to derive overall prediction scores. The simplified versions showed high discriminating power, with the areas under the receiver operating characteristic curve for DOATS and DOAT being 0.79 and 0.77, respectively, indicating their clinical utility. Although the original versions have a slightly higher predictive power, the new versions are easier to use in emergency situations; thus, importantly, selecting the appropriate version depends on the situation.

Although respiratory tract infection is a significant factor that triggers exacerbation of chronic obstructive pulmonary disease (COPD), the benefit of antibiotics for patients with COPD exacerbation remains controversial. It is necessary to evaluate the efficacy and safety of antibiotics versus placebo in such patients.

Airway stenting is an established procedure for treating oncological emergencies in patients with airway disorders. In patients with airway hemorrhage, respiratory conditions may worsen during stenting. Bronchial artery embolization (BAE) is useful to prevent bleeding from the bronchus. We aimed to evaluate the efficacy and safety of airway stenting after BAE in patients with malignant airway disorders.

Background: Peripheral intravenous catheters (PIVCs) are the most commonly used invasive medical device, yet despite best efforts by end-users, PIVCs experience unacceptably high early failure rates. We aimed to design a new PIVC that reduces the early failure rate of in-dwelling PIVCs and we conducted preliminary tests to assess its efficacy and safety in a porcine model of intravenous access.Methods: We used computer-aided design and simulation to create a PIVC with a ramped tip geometry, which directs the infused fluid away from the vein wall; we called the design the FloRamp™. We created FloRamp prototypes (test device) and tested them against a market-leading device (BD Insyte™; control device) in a highly-controlled setting with five insertion sites per device in four pigs. We measured resistance to infusion and visual infusion phlebitis (VIP) every 6 h and terminated the experiment at 48 h. Veins were harvested for histology and seven pathological markers were assessed.Results: Computer simulations showed that the optimum FloRamp tip reduced maximum endothelial shear stress by 60%, from 12.7 Pa to 5.1 Pa, compared to a typical PIVC tip and improved the infusion dynamics of saline in the blood stream. In the animal study, we found that 2/5 of the control devices were occluded after 24 h, whereas all test devices remained patent and functional. The FloRamp created less resistance to infusion (0.73 ± 0.81 vs 0.47 ± 0.50, p= 0.06) and lower VIP scores (0.60 ± 0.93 vs 0.31 ± 0.70, p= 0.09) than the control device, although neither findings were significantly different. Histopathology revealed that 5/7 of the assessed markers were lower in veins with the FloRamp.Conclusions: Herein we report preliminary assessment of a novel PIVC design, which could be advantageous in clinical settings through decreased device occlusion and reduced early failure rates.

Recombinant spider silk protein (RSP) is a promising biomaterial for developing high-performance materials independent of fossil fuels. In this study, we investigated the influence of the initial secondary structure of RSPs on the properties of RSP-based hydrogels. By altering the initial structure of RSP to β-sheets (β-RSP), α-helices (α-RSP), and random coils (rc-RSP) through solvent treatment, we compared the structures and mechanical properties of the resulting gels. Solid-state NMR revealed a β-sheet-rich structure in all gels, with the α-RSP gel exhibiting significantly higher strength and Young’s modulus compared to the rc-RSP gel. X-ray diffraction revealed that the α-RSP gel had a unique crystalline structure, distinguishing it from the β-RSP and rc-RSP gels. The different initial secondary structures possibly lead to variations in the crystalline and network structures of the molecular chains within the gels, explaining the superior mechanical properties observed in the α-RSP gels.

AbstractTreatment-resistant depression (TRD), defined as inadequate results after treatment with at least two antidepressants for 8 weeks, may be attributed to multiple factors, including the patient’s personality. In this research, we explored personality profiles based on egograms among 28 outpatients (22 men, 6 women) with TRD. Participants completed two self-questionnaires: the Tokyo University Egogram (TEG) and the Self Grow-up Egogram (SGE). Personality profiles showed the mean energy distribution among five ego states: Controlling Parent (CP), Nurturing Parent (NP), Adult (A), Free Child (FC), and Adapted Child (AC). In all 28 patients, the TEG and the SGE revealed a trough of FC and a peak of AC. SGE results showed a negative correlation between the Hamilton Rating Scale for depression score and FC energy. When patients were separated according to CP, egograms revealed low Adult energy in the low CP group and high Adult energy in the high CP group. Overall, this study indicated low FC energy and high AC energy in TRD and revealed two types of personalities with either low CP/low Adult energy or high CP/high Adult energy. These results should be considered in TRD therapy.

One of the major causes of oocyte quality deterioration, chromosome segregation abnormalities manifest mainly during meiosis I, which occurs before and during ovulation. However, currently, there is a technical limitation in the introduction of mRNA into premature oocytes without impairing embryonic developmental ability. In this study, we established a low-invasive electroporation (EP) method to introduce mRNA into pre-ovulatory, germinal vesicle (GV) mouse oocytes in an easier manner than the traditional microinjection method. The EP method with an optimized impedance value resulted in the efficient introduction of mRNAs encoding enhanced green fluorescent protein (EGFP) into the GV oocytes surrounded by cumulus cells at a survival rate of 95.0%. Furthermore, the introduction of histone H2B-EGFP mRNA into the GV oocytes labeled most of the oocytes without affecting the blastocyst development rate, indicating the feasibility of the visualization of oocyte chromosomal dynamics that enable us to assay chromosomal integrity in oocyte maturation and cell count in embryonic development. The establishment of this EP method offers extensive assays to select pre-implantation embryos and enables the surveying of essential factors for mammalian oocyte quality determination.The establishment of an electroporation method that ensures high survival and developmental rates breaks technical barriers to intervene premature oocytes, offering a future availability in preimplantation embryo treatment and assessment.Graphical Abstract

The presence of residual undifferentiated pluripotent stem cells (PSCs) in PSC-derived cell therapy products (CTPs) is a major safety issue for their clinical application, due to the potential risk of PSC-derived tumor formation. An international multidisciplinary multisite study to evaluate a droplet digital PCR (ddPCR) approach to detect residual undifferentiated PSCs in PSC-derived CTPs was conducted as part of the Health and Environmental Sciences Institute Cell Therapy-TRAcking, Circulation & Safety Technical Committee. To evaluate the use of ddPCR in quantifying residual iPSCs in a cell sample, different quantities of induced pluripotent stem cells (iPSCs) were spiked into a background of iPSC-derived cardiomyocytes (CMs) to mimic different concentrations of residual iPSCs. A one step reverse transcription ddPCR (RT-ddPCR) was performed to measure mRNA levels of several iPSC-specific markers and to evaluate the assay performance (precision, sensitivity, and specificity) between and within laboratories. The RT-ddPCR assay variability was initially assessed by measuring the same RNA samples across all participating facilities. Subsequently, each facility independently conducted the entire process, incorporating the spiking step, to discern the parameters influencing potential variability. Our results show that a RT-ddPCR assay targeting ESRG, LINC00678, and LIN28Agenes offers a highly sensitive and robust detection of impurities of iPSC-derived CMs and that the main contribution to variability between laboratories is the iPSC-spiking procedure, and not the RT-ddPCR. The RT-ddPCR assay would be generally applicable for tumorigenicity evaluation of PSC-derived CTPs with appropriate marker genes suitable for each CTP.Graphical Abstract

This paper presents a four-channel (4-ch) transmitter consisting of a 4-ch 65-nm CMOS cascode shunt laser diode (LD) driver and flip-chip-bonded 1.3-μm membrane LD-array-on-Si that has the highest power efficiency yet reported for 4-ch over-25-Gbps/ch transmitters that use distributed-feedback (DFB)-LDs and vertical-cavity surface emitting lasers. In order to transmit over-25-Gbps/ch NRZ PRBS-31 signals on four channels simultaneously, the driver incorporates electro-optic (EO)-response-improvement functions. It was designed with our photonic-electronic conversion system in SPICE, and the transmitter was implemented with a flip-chip-bonding interconnection between the driver and LD array. The effects of the EO-response-improvement functions were clarified mathematically and the optical output waveforms of a transmitter with and without the functions were simulated and measured. Furthermore, the bit error rate (BER) was measured. It was found that the functions improved the eye openings and reduced the jitter of the simulated and measured optical output waveforms. Moreover, the crosstalk penalties between discrete and simultaneous operation decreased, and 30 (31) Gbps/ch NRZ PRBS-31 signals could be transmitted error-free on four channels over 10-km-long standard single-mode fiber (or in the back-to-back (BtoB) configuration) with a power efficiency of 1.19 (1.15) mW/Gbps. Without the improvement functions, error-free simultaneous 4-ch transmissions were possible in the BtoB configuration for 25-Gbps/ch NRZ PRBS-31 signals but not for higher rates per channel.

Barium disilicide (BaSi2) is a thin-film solar cell material composed of abundant elements, and its application potential is further enhanced by its formation on inexpensive substrates, such as glass. The effect of the substrate temperature on the co-sputtering of BaSi2and Ba targets to form BaSi2films on Si(111) and TiN/glass substrates was investigated. Contrary to expectations, the photoresponsivity reached maximum values exceeding 5 and 2 A W–1, respectively, the highest value ever reported for as-deposited samples formed at 750 °C, more than 100 °C higher than those reported previously. Because the photoresponsivity is proportional to carrier lifetime, this result indicates that high-temperature growth can bring out the high performance of BaSi2as a light-absorbing layer. Because amorphous SiC (a-SiC) has a larger forbidden band gap and electron affinity than BaSi2, it is considered suitable as an electron transport layer (ETL) material for BaSi2solar cells. On the basis of this, the formation of BaSi2(absorption layer)/a-SiC (ETL)/TiN (electrode)/glass heterojunctions was also attempted, and the layered structure was examined by cross-sectional transmission electron microscopy (TEM). Polycrystalline BaSi2films were found to be even on the amorphous layer by TEM. A high photoresponsivity of over 2 A W–1was obtained. Therefore, the BaSi2/a-SiC/TiN structure provides a guideline for the structural design of BaSi2-based thin-film solar cells on glass.

In the pursuit of rapid atomic migration in lightweight Fe–Al diffusion couples, rationally designing short-circuit diffusion paths has become paramount. Herein, a strain-mediated defect engineering strategy was proposed for reducing the vacancy activation energy and enhancing diffusion behaviors along dislocations (DLs) and grain boundaries (GBs). Combining the modified Arrhenius-type relationship, an interfacial apparent activation energy of 139 kJ mol–1was acquired utilizing defect engineering, which was decreased by about 49%. This was closely related to high-density vacancies, DLs, and GBs formed in strained Fe and Al materials, which provided more low activation energy paths for atomic migration. First-principles calculations indicated that the lattice diffusion barrier mediated by monovacancy was reduced with strain incorporation, attributed to the weakened atom–vacancy bond as a consequence of less electron transport. The synergistic effect of abnormal electron-charge distribution in the bulk and strong attraction force at the Al/Fe interface radically resulted in rapid atomic migration, collectively regulating the “breaking–forming bond” process.

Human pancreatic cancer is characterized by the molecular diversity encompassing native duct-like and squamous cell-like identities, but mechanisms underlying squamous transdifferentiation have remained elusive. To comprehensively capture the molecular diversity of human pancreatic cancer, we here profiled 65 patient-derived pancreatic cancer organoid lines, including six adenosquamous carcinoma lines. H3K27me3-mediated erasure of the ductal lineage specifiers and hijacking of the TP63-driven squamous-cell programme drove squamous-cell commitment, providing survival benefit in a Wnt-deficient environment and hypoxic conditions. Gene engineering of normal pancreatic duct organoids revealed that GATA6 loss and a Wnt-deficient environment, in concert with genetic or hypoxia-mediated inactivation of KDM6A, facilitate squamous reprogramming, which in turn enhances environmental fitness. EZH2 inhibition counterbalanced the epigenetic bias and curbed the growth of adenosquamous cancer organoids. Our results demonstrate how an adversarial microenvironment dictates the molecular and histological evolution of human pancreatic cancer and provide insights into the principles and significance of lineage conversion in human cancer.

The change of fluorescence emission manipulated by spin state transition attracts considerable attention owing to its potential applications in magneto-optical switching devices. Herein, we report two two-dimensional (2D) Hofmann-type spin crossover (SCO) metal-organic frameworks (MOFs) [FeII(PNI)2{AgI(CN)2}2]·CHCl3(3Ag·CHCl3) and [FeII(PNI)2{AuI(CN)2}2]·CHCl3(3Au·CHCl3) based on the fluorescent ligand N-(4-pyridylmethyl)-1,8-naphthalimide (PNI). Both complexes exhibit interesting SCO behaviors switched by guest solvent molecules, namely three-step transitions for the solvated complexes and complete one-step hysteretic SCO for the desolvated ones, verified by temperature-dependent magnetic susceptibility measurements, Mossbauer spectra, structural analyses, and differential scanning calorimetry measurements. Correspondingly, temperature-dependent fluorescence spectra exhibit double peaks (monomer and excimer emission) with both emission peaks change consistent with the change in SCO properties during the solvent molecule removal. In this study, we integrated guest-responsive SCO behavior into MOFs to manipulate the multistability of spin state and fluorescence switching, providing a rational strategy for the development of stimuli-responsive multifunctional materials.

An estimated 12 million adults in the United States experience delayed diagnoses and other diagnostic errors annually. Ambulatory safety nets (ASNs) are an intervention to reduce delayed diagnoses by identifying patients with abnormal results overdue for follow-up using registries, workflow redesign, and patient navigation. The authors sought to co-design a collaborative and implement colorectal cancer (CRC) ASNs across various health care settings.

Food allergies are an increasing global problem and societal issue. In addition to the potential for severe allergic reactions from accidental ingestion, food allergies impose a significant burden on the quality of life, nutrition, cost of living, and social activities of both those afflicted and their caregivers. Strict avoidance of allergens and use of emergency medications to treat allergic reactions are the traditional management and treatment strategies; however, significant progress has been made in recent years toward better treatment of food allergies. Many clinical trials on food allergen immunotherapy (oral, epicutaneous, and sublingual) have revealed its efficacy in increasing reaction thresholds and desensitization. These positive results led to the first FDA approval of peanut oral immunotherapy (OIT). However, safer and more effective approaches are required, and adjunct treatments and allergen modifications are being considered. More than 100 facilities in Japan conduct OIT, and numerous studies on it have been reported. Unlike in Europe and the US, stepwise oral food challenges with dietary guidance are conducted separately from the OIT. This review describes the current perspectives on allergen immunotherapy for the treatment of food allergies, focusing on evidence from Japan.

Liver transplantation is often the only lifesaving option for acute liver failure (ALF); however, the predictors of short-term mortality (death within one year) after living donor liver transplantation (LDLT) for ALF have yet to be defined. We retrospectively collected patients ≥18 years old who underwent LDLT for ALF between 2010 and 2020 at 35 centers in Asia. Univariate and multivariate logistic regression analyses were conducted to identify the clinical variables related to short-term mortality and establish a novel scoring system. The Kaplan-Meier method was performed to explore the association between the score and overall survival. Of the 339 recipients, 46 (13.6%) died within 1 year after LDLT. Multivariate analyses revealed 4 independent risk factors for death: use of vasopressors or mechanical ventilation, the higher model for end-stage liver disease score, and a lower graft-to-recipient weight ratio. The internally validated c-statistic of the short-term mortality after transplant (SMT) score derived from these 4 variables was 0.80 (95% confidence interval: 0.74-0.87). The SMT score successfully stratified recipients into low-, intermediate-, and high-risk groups with 1-year overall survival rates of 96%, 80%, and 50%, respectively. In conclusion, our novel SMT score based on 4 predictors will guide ALF recipient and living donor selection.

Knowledge of the three-dimensional distribution of minerals in a rock sample is of fundamental importance to deciphering a sample’s properties and history. Attenuation-contrast X-ray computed tomography (X-ray CT) is widely used in the geosciences to determine the three-dimensional distributions of minerals or pores, or both. Photon counting CT (PC-CT) uses a novel energy-resolved X-ray detector that allows X-rays with a continuous energy spectrum to be detected separately within arbitrary energy ranges. Here we report the first results of applying laboratory-build PC-CT combined with multi-pixel photon counter (MPPC) to common minerals such as quartz and calcite. In the low-energy range, PC-CT produced higher contrast images than single-energy X-ray CT. Minerals were successfully identified from the relationships between the mean CT values for each energy window and the mean difference between pairs of energy windows. These results suggest that PC-CT can produce high-contrast images of minerals and may be able to distinguish mineral phases with different attenuation curves, even when their CT values are similar. We obtained CT images of minerals in a natural sedimentary rock sample, composed mainly of quartz and carbonate. Although the spatial resolution of the detector in this study was insufficient for the sample, the main carbonate veins were clearly visible as high carbonate-content areas in the PC-CT images. Given some prior knowledge of mineral phases from other methods, it may be possible to use PC-CT imaging to obtain further information about their chemical compositions.

Ni/Co-free high-energy positive electrode materials are of great importance to ensure the sustainability of Li-ion battery production and its supply chain in addition to minimizing environmental impact. Here, nanostructured LiMnO2with both orthorhombic/monoclinic layered domains is synthesized, and its lithium storage properties and mechanism are examined. High-energy mechanical milling is used to convert the metastable and nanosized LiMnO2adopting the cation-disordered rocksalt structure to an optimal domain-segregated layered LiMnO2. This positive electrode produces an energy density of 820 W h kg–1, achieved by harnessing a large reversible capacity with relatively small voltage hysteresis on electrochemical cycles. Moreover, voltage decay for cycling, as observed for Li-excess Mn-based electrode materials, is effectively mitigated. Furthermore, by determining the structure–property relationships of different LiMnO2polymorphs, LiMnO2with similar domain structure and surface area is successfully synthesized with an alternative and simpler method, without the metastable precursor and high-energy mechanical milling. The cyclability of domain-containing LiMnO2is also improved with the use of a highly concentrated electrolyte coupled with a lithium phosphate coating due to the suppression of Mn dissolution. These findings maximize the possibility of the development of high-energy, low-cost, and practical rechargeable batteries made from sustainable and abundant Mn sources without Ni/Co.

Retigerane-type sesterterpenoids, which feature a unique 5/6/5/5/5 fused pentacyclic structure with an angular-type triquinane moiety, are biosynthesized via successive carbocation-mediated reactions triggered by terpene cyclases. However, the precise biosynthetic pathways/mechanisms, wherein steric inversion of the carbon skeleton occurs at least once, remain elusive. Two plausible reaction pathways have been proposed, which differ in the order of ring cyclization: A → B/C → D/E-ring(s) (Route 1) and A → E → B → C/D-ring(s) (Route 2). Since the reaction intermediates of these complicated domino-type reaction sequences are experimentally inaccessible, we employed comprehensive density functional theory (DFT) calculations to evaluate these routes. The results indicate that retigeranin biosynthesis proceeds via Route 2 involving a multistep carbocation cascade, in which the order of ring cyclization (A → E → B → C/D) is the key to constructing the angular 5/5/5 triquinane structure with the correct stereochemistry at C3. The result also suggests that slight differences in the initial conformation have a significant effect on the order of cyclization and steric inversion. The computed pathway/mechanism also provides a rational basis for the formation of various related terpenes/terpenoids.

We present a novel approach to the formation of cell aggregates by employing click chemistry with water-soluble zwitterionic dibenzo cyclooctadiyne (WS-CODY) and azide-modified hyaluronic acid (HA-N3) as a linker to facilitate rapid and stable cell aggregation. By optimizing the concentrations of HA-N3and WS-CODY, we achieved efficient cross-linking between azide-modified cell surfaces and HA-N3, generating cell aggregates within 10 min, and the resulting aggregates remained stable for up to 5 days, with cell viability maintained at approximately 80%. Systematic experiments revealed that a stoichiometric balance between HA-N3and WS-CODY is important for effective cross-linking, highlighting the roles of both cell–surface azide modification and HA in the aggregate formation. We also investigated the genetic basis of altered cell behavior within these aggregates. Transcriptome analysis (RNA-seq) of aggregates postcultivation revealed a marked fluctuation of genes associated with ‘cell migration’ and ‘cell adhesion’, including notable changes in the expression of HYAL1, ICAM-1, CEACAM5and RHOB. These findings suggest that HA-N3-mediated cell aggregation can induce intrinsic cellular responses that not only facilitate cell aggregate formation but also modulate cell–matrix interactions. We term this phenomenon ‘chemo-resilience’, The simplicity and efficacy of this click chemistry-based approach suggest it may have broad applicability for forming cell aggregates and modulating cell–matrix interactions in tissue engineering and regenerative medicine.

We have achieved the enantioselective synthesis of highly strained, substituted o,m,o,p-tetraphenylenes (≤98% ee) via the cationic Rh(I)/(R)-H8-BINAP complex-catalyzed chemo-, regio-, and enantioselective intermolecular cross-[2+2+2] cycloaddition of teraryl diynes with dimethyl acetylenedicarboxylate. X-ray crystallographic analyses demonstrate the highly bent structures of the para-substituted benzene moieties, and density functional theory calculations reveal the large local strain of the paraphenylene unit. 1H nuclear magnetic resonance analyses and theoretical calculations elucidate the stereoisomerism, indicating that the nonrotatable ortho-disubstituted biphenyl structure results in cisand transisomers.

Singlet fission (SF) is a promising approach in quantum information science because it can generate spin-entangled quintet triplet pairs by photoexcitation independent of temperature. However, it is still challenging to rationally achieve quantum coherence at room temperature, which requires precise control of the orientation and dynamics of triplet pairs. Here we show that the quantum coherence of quintet multiexcitons can be achieved at room temperature by arranging two pentacene chromophores in parallel and in close proximity within a macrocycle. By making dynamic covalent Schiff-base bonds between aldehyde-modified pentacene derivatives, macrocyclic parallel dimer-1 (MPD-1) can be selectively synthesized in a high yield. MPD-1exhibits fast subpicosecond SF in polystyrene film and generates spin-polarized quintet multiexcitons. Furthermore, the coherence time T2of the MPD-1quintet is as long as 648 ns, even at room temperature. This macrocyclic parallel dimer strategy opens up new possibilities for future quantum applications using molecular multilevel qubits.

Performing operandospectroscopy under practical reaction conditions and extracting spectral components correlating with reaction activity are crucial in elucidating the reactive species in photocatalysis. However, the observation of weak signals corresponding to reactive photogenerated species is frequently hampered under reaction conditions owing to intense background signals originating from thermally induced species unrelated to the photoinduced reactions. Herein, by synchronizing the millisecond periodic excitations of photocatalysts with a Michelson interferometer used for FT–IR spectroscopy, we succeeded in significantly suppressing the signals derived from thermally excited electrons and observing the reactive photogenerated electrons contributing to the photocatalytic hydrogen evolution. This demonstration was achieved for metal-loaded oxide photocatalysts under steam methane reforming and water splitting conditions. Although it has long been conventionally believed that loaded metal cocatalysts function as sinks for reactive photogenerated electrons and active sites for reduction reactions, we found that the free electrons in the metal cocatalysts were not directly involved in the reduction reaction. Alternatively, the electrons shallowly trapped in the in-gap states of oxides contributed to enhancing the hydrogen evolution rate upon the loading of metal cocatalysts. We verified that the electron abundance in the in-gap states was clearly correlated to the reaction activity, suggesting that metal-induced semiconductor surface states formed in the periphery of the metal cocatalyst play key roles in the photocatalytic hydrogen evolution. Our microscopic insights shift a paradigm on the traditionally believed role of metal cocatalysts in photocatalysis and provide a fundamental basis for rational design of the metal/oxide interfaces as promising platforms for nonthermal hydrogen evolution.

The first isolation and characterization of transition metal complexes with the parent Al(I)–H unit were achieved in base-stabilized forms. W and Fe complexes, Cp*(CO)n(H)M←:AlH(NHC)2(NHC = N-heterocyclic carbene, n= 1 or 2), were synthesized in 43–63% yields by the one-step reaction of Cp*M(CO)n(py)Me with H3Al·NHC. The characterization included 1H and 27Al nuclear magnetic resonance (NMR), and infrared (IR) spectroscopic analysis, as well as DFT calculations, which revealed the extremely strong σ-donating ability of the :AlH(NHC)2ligand, and the highly polarized M(δ−)←:Al(δ+) coordination bonds. The monovalent oxidation state of the Al center of these complexes was confirmed by X-ray photoelectron spectroscopy (XPS). The hydroalumination of carbodiimide and the reduction of CO2to CO were also demonstrated.

ABSTRACTThe study investigated how social environmental factors (i.e., supportive behaviors of coaches and parents) are associated with thriving in sport amongst a youth population, influencing important outcomes of sport participation (i.e., intention to continue sport and subjective well-being in sport). Two-wave data was collected within a three-month time span to help determine the relationship of social environmental factors with intention to continue and subjective well-being. One hundred fifty-nine Japanese youth sport participants (Mage = 15.81) completed the questionnaires twice. Autonomy supportiveness of coaches and parents was positively related to thriving three months later. In contrast, only the relationship between autonomy support from coaches and thriving was mediated by the change in basic psychological need satisfaction. Moreover, autonomy support from coaches was related to intention to continue sport and subjective well-being in sport through the changes in basic psychological needs satisfaction and thriving individually and in sequence. The results indicate the importance of both the parent and coach in the role of nurturing the young athletes, while the influence was more robust for coaches. The findings indicate a need for stakeholders to focus on educating and promoting their role in creating supportive environments aimed at increasing retention and well-being.

X-ray therapy aims to eliminate tumours while minimizing side effects. Intense mucositis is sometimes induced when irradiating the oral cavity with a dental metal crown (DMC). However, the underlying mechanisms of such inducing radiosensitization by DMC remain uncertain. This study explored the radiosensitizing mechanisms around DMCs in an interdisciplinary approach with cell experiments and Monte Carlo simulation with the PHITS code. Clonogenic survival and nuclear 53BP1 foci of a cell line derived from cervical cancer cells (HeLa cells) were measured post-irradiation with therapeutic X-rays near high-Z materials such as Pb or Au plates, and the experimental sensitizer enhancement ratio (SER) was obtained. Meanwhile, the dose enhancement ratio (DER) and relative biological effectiveness for DNA damage yields were calculated using the PHITS code, by considering the corresponding experimental condition. The experiments show the experimental SER values for cell survival and 53BP1 foci near metals are 1.2–1.4, which agrees well with the calculated DER values. These suggest that the radiosensitizing effects near metal are predominantly attributed to the dose increase. In addition, as a preclinical evaluation, the spatial distributions of DER near DMC are calculated using Computed Tomography Digital Imaging and Communications in Medicine (CT-DICOM) data and a simple tooth model. As a result, the DER values evaluated using the CT-DICOM data were lower than those from a simple tooth model. These findings highlight the challenge of evaluating radiosensitizing effects near DMCs using Digital Imaging and Communications in Medicine (DICOM) images due to volume-averaging effects and emphasize the need for a high-resolution (<1 mm) dose assessment method unaffected by these effects.

Locomotive syndrome (LS) leads to reduced physical function and a high risk of becoming bedridden. Grip strength serves as an indicator of upper limb and overall physical function. Rheumatoid arthritis (RA) patients with reduced grip strength frequently show finger and wrist joint inflammation. The purpose of this study was to verify grip strength as an evaluation tool for physical function and LS in RA patients.

Advanced sensing technologies such as remote sensing and sensor networks, important for enhancing land use through soil condition monitoring, are facing issues including high machine learning costs, limited measurement point density, and environmental impact. This study introduces a remote sensing method that offers both direct and wide-area sensing of soil properties using a dispersible, biodegradable cuboid-shaped isotropic metamaterial equipped with a water-soluble Mg-based resonance antenna structure. The symmetrical metal patterns ensure isotropic reflectance within the 1.2–3.6-GHz range, enabling robust sensing even when the metamaterial is dispersed randomly on the soil. The degradation of the Mg antenna in the soil presents a significant reflection reduction from 80% to 20% at a 2.4-GHz resonant frequency on the soil, promoting the feasibility of combination with a simple wireless measurement system. Integration with functional coatings that dissolve in response to specific soil substances such as pH-sensitive hydroxyapatite leads to the development of biodegradable soil remote monitoring sensors, offering precise, sustainable land management.