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The comparative analysis of Sino-Japanese football policies from the perspective of policy instruments
Football development depends heavily on strong policy support, rendering policy analysis and evaluation of significant practical importance. This study uses Nvivo11 software and the PMC index model to conduct a quantitative comparative analysis of 31 Sino-Japanese football policy texts, focusing on policy instruments, content characteristics, and overall quality. The findings reveal that both countries prioritize football development, social participation, and club construction; China emphasizes campus football, while Japan focuses on elite player development and league performance. PMC evaluation indicates that Chinese policies score higher in system design and institutional capacity, whereas Japan performs better in implementation clarity and community linkage. Both countries share shortcomings in insufficient policy clarity and vague long-term competitive goals. The research results provide empirical evidence for the optimization of Chinese football policies and a reference for drawing on international experience.
Pattern of opioid prescriptions among patients with breast, lung, and colorectal cancer diagnosed with pre-existing chronic non-cancer pain
Background Chronic non-cancer pain (CNCP) due to comorbid conditions presents a barrier to optimal pain management in patients with cancer. While opioid is widely used for the treatment and management of CNCP, it is also associated with misuse and addictions. Therefore, we determined the impact of CNCP on opioid prescribing patterns in patients with the three most common cancer types- breast, lung, and colorectal cancers. Methods A retrospective cohort study was conducted utilizing Surveillance Epidemiology and End Results (SEER)-Medicare (2006–2019) linked database. Patients, at least 66 years old with histologically confirmed incidental diagnoses of breast, lung, or colorectal cancer from 2007 to 2017, were included in the study. Patients with cancer in baseline period, in palliative care, or those who died in the follow-up period were excluded from the study. Patients with CNCP were identified in the baseline period. Patients without CNCP during the study period were included in the no-CNCP group. The follow-up period was one year after cancer diagnosis (index date) and the primary outcome was opioid prescribing patterns defined as: any opioid use, high-dose opioid use, total count of opioid prescriptions filled, and chronic opioid use. Inverse probability weighting (IPTW) method was used to balance the covariates (age at the cancer diagnosis time, sex, race, ethnicity, marital status, cancer type, cancer stage, metropolitan status, year of cancer diagnosis, chronic cancer-treatment-related pain, neoplasm pain, and cancer treatment modalities) between the CNCP and no-CNCP group. Logistic and Poisson regressions were used to compare opioid use and opioid prescription patterns among the two groups. Results A majority of patients included in the study were breast cancer (CNCP = 38230, no-CNCP = 56157), lung cancer (CNCP = 17255, no-CNCP = 24602), colorectal cancer (CNCP = 16660, no-CNCP = 29037). Among cancer patients, the prevalence of CNCP was highest in those with lung cancer (41.2%) followed by breast cancer (40.1%) and colorectal cancer (36.4%). Descriptive analysis demonstrated patients with lung cancer had consistently higher rates across opioid prescribing patterns, followed by patients with colorectal and breast cancer. The result of logistic regression after weighting showed that the odds of any opioid use were higher among lung cancer patients with CNCP (OR 1.5; 95% CI 1.5–1.6; p < 0.01) compared to the no-CNCP group with lung cancer. Patients with breast cancer and CNCP had higher odds of chronic opioid use followed by lung cancer and colorectal cancer (OR 2.7; 95% CI 2.6–2.8; p < 0.01, OR 2.4, 95% CI 2.3–2.5; p < 0.01, and OR 2.4; 95% CI 2.3–2.5; p < 0.01) respectively compared to patients without CNCP but respective cancer. Conclusion CNCP adds an additional burden in opioid prescription in active cancer patients which necessitates a meticulous approach to opioids prescribing.
Examining the joint impact of missing data mechanisms and item parameter drift on the accuracy of item response theory-based test equating
Maintaining score comparability across different test administrations is essential in large-scale educational and psychological assessment. Two major threats to equating accuracy are item parameter drift (IPD), reflecting changes in anchor item characteristics over time, and missing item responses, which commonly occur in operational testing. Although each factor has been studied separately, their joint impact on equating accuracy has not been systematically evaluated. A Monte Carlo simulation was conducted using a nonequivalent groups with anchor test design. Data were generated under a three-parameter logistic model with 2,000 examinees per form and 500 replications per condition. The Stocking–Lord method was used to estimate equating constants across 25 conditions, varying IPD rate (0%, 10%, 20%), IPD magnitude (0, 0.25, 0.50), missing data mechanism (MCAR vs. MAR), and missing data rate (0%, 10%, 20%). Missing responses were addressed using multiple imputation by chained equations. Equating accuracy was evaluated using bias and root mean square error. Results indicated that the B constant was highly sensitive to the missing data mechanism: MCAR conditions produced near-zero bias, whereas MAR conditions introduced substantial positive bias, particularly at higher missing rates. IPD alone did not result in meaningful bias but increased estimation variability. When IPD and MAR co-occurred, equating error exceeded the sum of their individual effects, indicating an interaction rather than a purely additive relationship. Although multiple imputation reduced error under MCAR, it did not fully eliminate bias under MAR conditions. In contrast, the scale constant remained stable across all conditions. Overall, the missing data mechanism had a stronger impact on equating accuracy than either the rate of missingness or the degree of item drift alone. When both factors were present, their combined influence led to increased error that could not be fully corrected through imputation. These findings underscore the importance of carefully evaluating missing data mechanisms, selecting appropriate imputation strategies, such as MICE, and monitoring anchor item stability to ensure accurate score equating, particularly in psychological assessment contexts where even small errors may affect individual-level decisions.
Dual biocontrol and osmotic stress mitigation by endophytic Aspergillus micronesiensis and Penicillium momoi against fusarium pathogens
Global challenges associated with crop diseases and abiotic stress necessitate sustainable agricultural solutions. This study investigated the biocontrol and osmotic-stress mitigation potential of two endophytic fungi, which were isolated from native plants and subsequently identified as Aspergillus micronesiensis and Penicillium momoi . Their antagonistic activities against Fusarium oxysporum f. sp. lycopersici (FOL), F. oxysporum f. sp. radicis-lycopersici (FORL), and F. pseudograminearum (FPS) were evaluated. Complementary antagonistic mechanisms were observed: P. momoi primarily inhibited pathogen growth through direct mycelial competition, while A. micronesiensis predominantly exerted effects through antibiosis. In dual-culture assays, A. micronesiensis inhibited FOL, FORL, and FPS by 39.05%, 39.93%, and 54.59%, respectively, whereas P. momoi caused inhibition rates of 51.84%, 64.74%, and 60.66%, respectively, demonstrating strong biocontrol potential. The salt tolerance assay revealed that both endophytes were able to grow on media containing up to 3 M NaCl. Although, optimal growth for both isolates occurred at 1 M NaCl, A. micronesiensis showed a greater increase in growth relative to the control (2.06 times). In contrast, P. momoi maintained more consistent growth across the 0–1 M NaCl range. However, growth of both isolates declined at higher salt concentrations. The developed wettable powder formulation maintained high spore viability for at least 27 months under room-temperature conditions. This research highlights A. micronesiensis and P. momoi as promising agents for managing Fusarium diseases and enhancing plant salinity tolerance. Further metabolomics investigations are recommended to clarify the functional roles of these endophytes in crop protection under stress conditions.
Systematic multi-parameter optimization of an injectable thermosensitive CS/β-GP/HEC hydrogel for 3D cell culture applications
Injectable thermosensitive hydrogels have been widely investigated as minimally invasive scaffolds for three-dimensional (3D) cell culture. In this study, we systematically screened a chitosan (CS)/β-glycerophosphate (β-GP)/hydroxyethyl cellulose (HEC) ternary hydrogel system using a 2 × 2 × 2 factorial design. By evaluating gelation kinetics, injectability, and structural stability through a weighted scoring model, two superior formulations (G1 and G3) were selected for their ability to balance rapid gelation at 37 °C with reliable room-temperature injectability. Subsequent biological evaluations demonstrated that, compared to conventional 2D cultures, the 3D hydrogels supported robust cellular viability and spatial proliferation through Day 10. The stable biomimetic matrix provided essential physical anchorage, enabling Huh7 cells to self-assemble into dense tumor spheroids and BMSCs to establish spatial networks. This study presents a structured formulation-screening strategy and demonstrates the effectiveness of the CS/β-GP/HEC hydrogel as a reliable platform for in vitro 3D cell culture applications.
Efficacy and safety of prebiotics, probiotics, and synbiotics on hemoglobin and anemia in the pediatric population: A systematic review and meta-analysis
Aim To evaluate the efficacy and safety of prebiotics, probiotics, and synbiotics on hemoglobin levels and anemia in the pediatric population. Methods We conducted a systematic review and meta-analysis of randomized clinical trials (RCTs). PubMed, Embase, and CENTRAL were searched up to August 2025. We included RCTs assessing prebiotics, probiotics, or synbiotics on hemoglobin or anemia in children. Random-effects meta-analyses were performed, and certainty of evidence was assessed using GRADE and minimal important differences. The protocol was registered in PROSPERO (CRD420251108276). Results Nineteen RCTs involving 4188 children were included. Compared to placebo or standard care, prebiotics, probiotics, and synbiotics (alone or with iron) showed no important effects on hemoglobin, hematocrit, or ferritin (certainty: high to very low). However, probiotics versus placebo may reduce anemia (1 RCT; RD: -−6 per 100; 95% CI: -−15 to +6, low certainty). No serious adverse events were reported; observed events were mainly mild gastrointestinal symptoms. Conclusion Prebiotics, probiotics, and synbiotics do not provide clinically important benefits on hemoglobin or anemia in children, although they appear safe. Larger, high-quality trials in high-risk populations are needed.
Chiral 3d–4f Clusters with NIR-III Magneto-Optical Activity Driven by Lanthanide f–f Transition
Abstract Chiral molecular materials with strong magneto-optical responses in the near-infrared III (NIR-III, 1600–2500 nm) region are attractive for applications in photonics, biomedicine, and advanced optical materials, but molecular magneto-optical phenomena in this spectral window remain largely unexplored. Here, we report six pairs of chiral 3d–4f molecular clusters, R/S-Ln3Mn4 and R/S-Ln12Mn12 (Ln = HoIII, TbIII, and YIII), and systematically investigate their chiroptical and magneto-optical properties in the NIR-III region. Circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopy reveal that R/S-Ho3Mn4 and R/S-Ho12Mn12 clusters exhibit pronounced CD and MCD responses in the NIR-III region arising from long-wavelength HoIII f–f transitions, whereas R/S-Tb3Mn4 and R/S-Tb12Mn12 show strong MCD responses but no resolved CD signals. These findings identify long-wavelength lanthanide f–f transitions as the origin of the NIR-III chiroptical and magneto-optical activity. Notably, the R/S-Ln12Mn12 series exhibits larger gMCD values and stronger NIR-III MCD responses than the corresponding R/S-Ln3Mn4 analogues. This enhancement may arise from the change in local LnIII coordination geometry from D4d in Ln3Mn4 to D2d in Ln12Mn12, which favors a stronger Zeeman-perturbed MCD response, along with cooperative LnIII-MnII weak magnetic interactions in Ln12Mn12. This work provides the first molecular example of f–f-transition-driven chiroptical and magneto-optical activity across the NIR-III window and establishes chiral 3d–4f clusters as structurally defined platforms for tuning long-wavelength magneto-optical responses.
General healthcare preferences for people aged 50 and over in England: English longitudinal study of ageing
Background Treatment outcomes and satisfaction improve when healthcare decisions align with patient preferences. However, little is known about general health preferences in older adults, and eliciting patient preferences is time consuming. Aim To describe the distribution of preferences for healthcare in general, and associations between preferences and patient characteristics in adults aged 50 years and over in England. Design and setting Data were collected in wave 8 (2016/2017) of the English Longitudinal Study of Ageing (ELSA), a biennial longitudinal survey of people aged 50 and over living in private households in England that began in 2002/2003 and is designed to be nationally representative. Method Data were collected from ELSA participants using face-to-face interviews and a short self completion questionnaire. Amongst other items, the questionnaire contained six measures of general healthcare preferences that had not been asked in previous ELSA waves: risk aversion, future orientation, quality or length of life, body function compared to looks, openness to experimental treatments, and preference to leave treatment decisions to a doctor. Results Healthcare preferences varied substantially, with some systematic patterns by age and sex: women were less likely than men to want to delegate decisions to doctors, and more likely to prioritise quality of life over length of life; participants aged over 75 years were more likely than younger participants to want to delegate decisions to doctors, and more likely to want to avoid risks. Conclusion The systematic sex and age differences offer a useful starting point for eliciting healthcare preferences in a busy clinical environment, but cannot replace asking about individual preferences.
Smart Pickering Emulsions Co-Stabilized by Chalcogenoviologen Surfactants and Single-Atom Pt-Decorated g-C3N4 for Switchable Biphasic Photocatalysis
Abstract Interfacial reaction microenvironments play a critical role in determining photocatalytic performance beyond the intrinsic properties of photocatalysts. However, emulsion-based photocatalytic platforms that simultaneously offer structural robustness, switchable operation, and efficient interfacial charge-transfer regulation remain rare. Herein, smart-responsive Pickering emulsions are developed by costabilization of chalcogenoviologen surfactants (SV2+-UDA/SeV2+-UDA/TeV2+-UDA) and single-atom platinum-decorated graphitic carbon nitride (Pt SAs@g-C3N4) for biphasic photocatalysis. The resulting emulsions exhibit outstanding stability in strong acidic and alkaline media as well as in saturated brine while allowing reversible demulsification and re-emulsification under an external electric field, thereby enabling switchable catalysis and catalyst recovery. The optimized emulsion achieves a hydrogen evolution rate of up to 7824 μmol·h–1·g–1 under visible-light irradiation, corresponding to a 3.0-fold enhancement over the bulk aqueous, viologen-free system, while retaining over 90% of its activity across a wide pH range and under seawater salinity. More importantly, the emulsion functions as a bidirectional microreactor, coupling aqueous hydrogen evolution with oil-phase oxidative coupling of benzylamine without sacrificial reagents, and delivers imine yields above 85% together with a hydrogen evolution rate of 3892 μmol·h–1·g–1. The enhanced performance highlights the critical role of interfacial synergy. The surfactant/photocatalyst costabilization strategy provides a versatile platform for robust, switchable, and synergistic biphasic photocatalysis.
Pronunciation assessment in foreign language learning: Reliability and scoring bias in human–generative AI evaluation
This study examines the reliability and scoring bias of generative AI (Gen-AI)-based pronunciation assessment compared with human raters, addressing whether AI-generated scores can be trusted in real educational settings. Sixty students participated in a 12-week program. A total of 180 pronunciation samples were evaluated across eight subcomponents (individual phonemes, stress, rhythm, intonation, linking, reduction, fluency, and clarity) by three standardized human raters and Gen-AI using the same 7-point rubric. Quantitative analyses (intraclass correlation coefficients, paired-samples t-tests, and Pearson correlations) assessed reliability and bias, while semi-structured interviews with raters provided explanatory qualitative insights. Gen-AI demonstrated moderate reliability with human raters across most components, showing the highest agreement in fluency and the weakest in individual phonemes. However, Gen-AI consistently assigned significantly higher scores than human raters across all subcomponents. Qualitative findings revealed that discrepancies originated from Gen-AI’s limited discriminative power, systematic flaws in handling missing data, decontextualized scoring approach, lack of sensitivity to L1 interference, and inability to interpret pragmatic context. While Gen-AI cannot fully replace human expertise, it can function as a complementary tool for formative assessment and autonomous practice. A hybrid assessment model integrating Gen-AI’s efficiency with human raters’ contextual and interpretive insights is recommended for effective foreign language pronunciation education.
From productive landscape to cultural space: The heterogeneous coupling of heritage value perception and tourist experience demand in the Grand Canal Cultural Route
In the context of rapid urbanization, the transformation of linear hydraulic heritage from productive landscapes to high-quality cultural spaces is a pivotal issue for sustainable development. Taking the Huai’an section of the China Grand Canal as a case study, this research explores the coupling mechanism between heritage value perception and tourist experience demand within a non-Western cultural route. Addressing the insufficient attention paid by existing literature to the dynamic evolution of production-and-transport heritage, this study adopts a systems theory perspective. It utilizes Canonical Correlation Analysis (CCA) to reveal the holistic mapping relationship between two sets of multidimensional variables. The findings indicate that the relationship between heritage value perception and experience demand is not a simple linear correspondence, but rather a significant heterogenetic driving mechanism. Particularly, the strong coupling effect of narrative value and the spirit of place on educational experience demands identifies the core variables through which Grain Transport Cultural Route enhances local identity and spatial perception. The study further reveals the constraints of social stratification on heritage consumption, confirming the moderating effects of cultural capital and social background in the “perception-demand” transformation process. By challenging static preservation views, this study proposes a dynamic, multidimensional evolutionary model of heritage cognition. It provides an analytical framework and policy guidelines for soft-power transformation and segmented protection of linear heritage in non-European contexts, offering a significant theoretical contribution to heritage functional activation in urban sustainable development.
Tracing early life stress in human molar morphology: Associations between linear enamel hypoplasia and maxillary first molar form
Permanent tooth structures can respond to environmental disruptions even after the initiation of hard tissue deposition at the cusp tips, affecting dental morphology. In bioarcheological studies, linear enamel hypoplasia (LEH) provides evidence of both the presence and timing of developmental stressors that can occur during first molar odontogenesis. Yet, previous studies used LEH from the entirety of the anterior tooth surface to relate disruptions to changes in permanent tooth morphology, which could conflate causality by misrepresenting the timing of events. This study assessed associations between LEH formed during maxillary permanent first molar development and dental characteristics of these molars in contemporary humans with known health and nutritional histories from Tezonteopan, Mexico. LEH were observed in the field, and dental characteristics (crown size, principal cusp spacing, expression of cusp 5 and Carabelli trait) were observed on maxillary dental casts taken of the same adolescent study participants (n = 54). Statistical analyses included multivariate- and generalized linear models, and Principal Component Analyses. Slightly larger crown sizes, decreased buccolingual principal cusp spacing, and a slight decrease in cusp 5 expression were associated with the presence of LEH. The decrease in cusp spacing and decrease in cusp 5 expression follow expectations of the Patterning Cascade Model. Our results differ in some ways from those of previous studies possibly due to our focus on LEH defects forming during molar developmental periods. Our findings support the growing body of studies highlighting the unpredictability of molar morphology in the presence of developmental disruptions.
Chemically Separable Ruthenium Hydride Isomers with Distinct Hydride Transfer Properties
Abstract Transition metal hydrides are key intermediates in biological and industrial catalysis, where control over hydride donor ability (hydricity) is essential for optimizing reactivity. Herein, we report a series of isomeric ruthenium hydrides in which the ligand trans to the ruthenium hydride bond–either an N-heterocyclic carbene or pyridine–modulates the thermodynamic hydricity by up to 8 kcal mol–1. These hydrides exhibited distinct reactivity toward CO2 and various organic hydride acceptors, enabling detailed kinetic and mechanistic analysis. Stopped-flow experiments, isotopic labeling, and computational studies supported an outer-sphere hydride transfer mechanism. Linear free energy relationships (LFERs) and Marcus relationships were utilized to correlate the changes in thermodynamics and kinetics, revealing that ligands with strong trans effects and trans influence can disrupt conventional scaling relationships, which can be a powerful strategy for promoting new reactivity paradigms in hydride transfer reactions.
Dopaminergic genetic variation and response to social comparative feedback when learning a motor sequence task
Positive social comparative feedback during motor skill practice is hypothesized to enhance motor learning by triggering a dopaminergic response. Individual differences in dopamine-related genes impact dopamine neurotransmission and may influence responsiveness to motor practice conditions that target dopaminergic pathways. The purpose of this study was to examine the impact of dopamine genotype on learning of a motor sequence task under two different feedback conditions: response time only feedback or response time with positive social comparison. Fifty-two adults practiced a joystick-based motor sequence task over two consecutive days. On Day 1, participants were randomized to receive either 1) response time only feedback (i.e., “You completed the block in 80 seconds”) or 2) positive social comparative feedback (i.e., “You completed the block in 80 seconds. You were faster than others”). Motor learning was assessed by retention performance, or the change in response time from the first block of Day 1 to the first block on Day 2. Saliva samples were used to genotype for dopamine receptors DRD1, DRD2 and DRD3 and COMT. Individual genes were scored (0–2) and summed to create a polygene score (0–8). Participants were then categorized as having Low (1–4) or High (5–8) dopamine neurotransmission. A significant interaction was found between time, summary polygene group and feedback group (p = 0.048). The Low dopamine group showed greater improvements with response time only feedback versus positive social comparative feedback. The High dopamine group showed similar improvements in response time regardless of feedback type. This suggests that feedback targeting dopaminergic pathways may not be beneficial for individuals with lower dopamine neurotransmission. Our findings suggest that dopaminergic genetics may impact the efficacy of positive social comparative feedback on motor learning in low dopamine genotypes.
Computational analysis reveals historical trajectory of East Polynesian lunar calendars
We investigate a type of lunar calendar known as lists of the ‘nights of the moon’, found throughout East Polynesia, including Rapa Nui (Easter Island). Using computational methods, we analyzed the lexical and structural divergence of 48 calendrical lists from all major archipelagos, each containing about 30 night names. Our results, presented as a rooted phylogenetic tree, show a split into two main groups: one including lists from Rapa Nui, Mangareva, and the Marquesas; the other comprising lists from New Zealand, Hawai’i, the Cook Islands, the Austral Islands, Tahiti, and the Tuamotu. This result aligns with a recent alternative classification of East Polynesian languages into ‘Distal’ (Marquesan, Mangarevan, Rapanui) and ’Proximal’ (Māori, Hawaiian, Tahitian, etc.) subgroups. Since both language and lunar calendars are symbolic systems passed down and changed within communities—and given the geographic isolation of many archipelagos—we interpret this correspondence as evidence that the early divergence of East Polynesian lunar calendars mirrors early population movements and language splits in the region.
Coverage-Dependent Lateral Interactions Shape the Electrocatalytic Activity of High-Entropy Alloys
Abstract While the rich diversity of surface sites on high-entropy alloys (HEAs) is essential for tuning electrocatalytic activity, the coverage-dependent lateral interactions that shape reactive interfaces are often neglected in theoretical studies. Here, we develop a machine learning interatomic potential (MLIP)-enabled framework to model the oxygen reduction reaction (ORR) within an Ag–Ir–Ru–Pd–Pt–Cu–Rh–Re alloy composition space. By tracking the binding strengths of O* and OH* intermediates during competitive coadsorption on crowded surfaces, this framework highlights the key role of lateral interactions, including attractive hydrogen-bond networks and electrostatic repulsion, in evaluating electrocatalytic activity. Incorporating these coverage-induced effects improves agreement with reported PtIr and AgPd composition–activity trends relative to an isolated-site baseline. We further show that increasing compositional complexity within the studied alloy space can amplify lateral repulsion under finite-coverage conditions, broadening binding strength distributions and reducing the population of optimal active sites. The competition between local electronic optimization and coverage-dependent lateral interactions gives rise to a volcano-shaped activity–entropy relationship, offering guidance for the rational design of HEA-based ORR electrocatalysts.
Drug use patterns at a Kenyan referral hospital: A cross-sectional study using WHO core indicators
Background Suboptimal medicine use practices remain a major global health challenge, particularly in low- and middle-income countries, where it contributes to increased healthcare costs, and the growing burden of antimicrobial resistance. This study aimed to evaluate drug use patterns at Thika Level 5 Hospital in Kenya using World Health Organization (WHO) core drug use indicators. Methods A facility-based cross-sectional study was conducted in the outpatient department. Data were collected from 600 prescriptions, 100 patient encounters, and facility-level assessments using standardized WHO/INRUD data collection tools. Descriptive and inferential analyses were performed using IBM SPSS Statistics (version 29), and findings were descriptively compared with WHO reference standards. Results The mean number of drugs per prescription was 3.18, which was higher than the WHO recommended range of 1.6–1.8. Generic prescribing was 45.86% while antibiotic prescribing was observed in 58.7% of encounters. Injection use was 13.0% and 76.86% of prescribed medicines were from the Essential Medicines List (EML). Patient-care indicators showed a mean consultation time of 4.26 minutes and a mean dispensing time of 122.8 seconds, which was below the WHO- recommended reference value. Only 30.0% of medicines were adequately labelled, and 44.0% of patients demonstrated complete knowledge of their medications. Significant associations were observed between dispensing time and patient knowledge (p = 0.001), as well as between labelling adequacy and patient understanding (p < 0.001). In contrast, all facility indicators met WHO standards, with full availability of essential medicines, treatment guidelines, and stock records. Conclusion Despite strong facility readiness, important gaps were identified in prescribing and patient-care practices. These findings highlight opportunities for interventions aimed at strengthening antimicrobial stewardship initiatives, promoting generic prescribing, improving dispensing practices, and enhancing patient counselling to support improved medicine use practices..
Droplet-Enhanced Asymmetric Catalysis: Squaramide-Derived Pseudopeptide for Enantioselective Addition Reactions
Abstract Droplets formed through phase separation represent an emerging strategy to enhance enzyme-mimetic catalysis, demonstrating significant potential in catalytic science. However, due to the lack of systematic methodologies for precise engineering of chiral microenvironments within droplets, their application to asymmetric catalysis remains largely unexplored. To address this challenge, we integrate l-phenylalanine into an L-tert-leucine-derived squaramide to design the squaramide-derived pseudopeptide droplets. This catalytic system demonstrates remarkably enhanced catalytic performance in the enantioselective conjugate addition of α-nitrosulfone to acrylates and enones, as well as Michael addition of acetylacetone to β-nitroalkenes. Mechanistic investigations reveal that the increased local substrate concentration significantly enhances reactivity, while the engineered favorable chiral microenvironment boosts enantioselectivity. This study establishes a methodological framework for elucidating differentiated catalytic behaviors within the droplets, thereby advancing the design and application of droplet-based asymmetric catalytic systems.
Water-Mediated Ion Selectivity in 2D MXene Channels
Abstract At the Ångström scale, water confined between two-dimensional layers behaves fundamentally differently from bulk water; this behavior governs ion transport in natural and engineered nanofluidic systems, yet the mechanisms by which confined water mediates selective ion transport remain poorly understood. As classical descriptions of aqueous ion transport break down under extreme confinement, experimental studies often face challenges in controlling both nanoconfined structure and surface chemistry, limiting our ability to explain and predict water and ion behavior in subnanometer channels and membranes. Here, we show that 2D Ti3C2Tx MXene nanosheets with precisely controlled interlayer spacing (0.9–5.0 Å), surface terminations, and electrode potentials provide a platform to systematically tune ion transport. Combined experimental measurements, including ion permeation, spatial secondary-ion mass spectrometry, and Fourier transform infrared spectroscopy, together with molecular dynamics simulations, reveal that ultranarrow confinement reorganizes confined water, imposes ion-specific energetic penalties for dehydration, and modulates ion–MXene interactions. Li+ permeation in horizontally aligned Ti3C2Tx channels is 2 orders of magnitude faster than in conventional vertically aligned MXene membranes, while electrochemical surface charge modulation further regulates ion selectivity. These coupled effects of confinement, surface chemistry, and water-mediated energetics define a transport regime beyond classical diffusion, offering design principles for artificial ion channels and high-performance membranes for ion separation, water desalination, and sustainable water treatment technologies.
Procedural or declarative deficit in adults with developmental dyslexia? A study of Artificial grammar learning
Artificial grammar learning (AGL) has frequently been employed to investigate the procedural hypothesis of dyslexia. However, most studies did not distinguish whether performance depended upon the acquisition of grammatical rules (procedural memory), distributional knowledge (statistical learning) or reference to individual memory traces (instances). An AGL paradigm was administered to 32 young adults with dyslexia and 60 controls. During the learning phase, adults with dyslexia learned artificial grammar and then utilized procedural memory in the grammaticality judgment and recognition tasks to a similar extent as controls. An overall group difference was observed only on the grammaticality judgment task; however, the performance of both groups was similarly modulated by the grammaticality of the stimuli. Adults with dyslexia acquired and used individual memories (instances) in both grammaticality judgment and recognition tasks. However, they exhibited some difficulty in forming individual memories, as indicated by their greater tendency to mistakenly identify non-grammatical control items as previously seen during the training phase (recognition task). On untrained items, adults with dyslexia also showed an advantage with high compared to low-bigram frequency stimuli, indicating reliance on sublexical statistical cues to foster their performance. In conclusion, adults with dyslexia acquired procedural rules and showed sensitivity to the distributional properties of the stimuli, providing little support for the procedural hypothesis of dyslexia. This study highlighted both spared and compensatory mechanisms in adults with dyslexia. Previous conflicting results may depend on not having isolated which components (procedural vs declarative memory vs statistical learning) are involved in the AGL paradigm.