Browse Articles

Highly Efficient Mechanochromic Thermally Activated Delayed Fluorescence in the Deep Red to Near‐Infrared in Copper(I) [2.2]Isoindolinophanyl‐Carbene Carbazolates

ABSTRACT Low energy triplet emitters are highly relevant for the development of OLEDs and fiber optics‐based IT applications, but typically suffer from nonradiative decay due to the energy gap law (EGL). Excited state deactivation can be limited by enhancing the radiative decay rate via thermally activated delayed fluorescence (TADF), bypassing spin‐forbidden phosphorescence. We report on linear copper(I) complexes bearing a recently reported [2.2]isoindolinophanyl‐carbene (iPC) ligand as potent excited state π‐acceptor. The compounds show efficient TADF from ligand‐to‐ligand charge transfer ( 1/3 LLCT) states with reverse intersystem‐crossing (RISC) of k RISC = 0.6–21·10 9 s −1 , quantum yields of up to 0.8 and k TADF of 0.8‐1.9·10 6 s −1 that are among the fastest for Cu I emitters, outcompeting traditional triplet emitters based on Ir III and Pt II as well as organic deep red to near‐IR TADF emitters. While yellow to red emission is observed in single crystals, embedding the complexes into polymers or grinding shifts the luminescence into the deep red to near‐IR. The mechanochromism is due to disruption of C─H⋯π interactions between the ligands, reducing the energy gap between the ground state and 1/3 LLCT states. The Cu I iPC complexes bear potential for devices operating under electroluminescent conditions as demonstrated by a proof‐of‐concept deep‐red OLED application.

<i>o</i> ‐Terphenyl‐Based Family of Conjugated Macrocycles: Selective Recognition of Phenylalanine in Water and Interaction With Insulin

ABSTRACT The design of supramolecular receptors for amino acids presents a fundamentally challenging yet highly promising avenue of research. Phenylalanine attracts special attention because of its multifaceted role in living organisms. Although many synthetic hosts have been explored for recognition of phenylalanine (Phe), besides cucurbiturils, there are no receptors that show selectivity for Phe over other aromatic amino acids and related aromatic neurotransmitters in water. Toward addressing this challenge, we explored pi‐conjugated water‐soluble macrocycles with hydrophobic pockets. A new family of o ‐terphenyl‐based macrocycles, TP[n] ( n = 2‐8) was synthesized using the Yamamoto reaction. Macrocycles up to the octamer, TP[2]‐TP[8], were isolated and fully characterized. X‐ray studies reveal that these macrocycles can form folded conformations stabilized by stacking interactions. TP[3] was identified as the most selective host for Phe with an affinity of 7 x 10 3 M −1 in water. The hosts, composed of 2–5 subunits were found to effectively inhibit protein aggregation according to the fluorescence assay using thioflavin T. The discovery of the new family of macrocycles paves the way for designing hosts with diverse architectures, precisely tailored geometries, and optimized binding properties capable of targeting not only individual amino acids but also entire protein surfaces.

Guidelines for selecting variability measure in limited-size ANOVA experiments

Abstract Graphical representation of variability is essential for accurately communicating scientific results in applied sciences. In ANOVA experiments with a low number of replicates (n), the selection between pooled or individual standard deviations (SDs) poses a methodological challenge. The aim of this study is to offer practical guidelines to help researchers decide whether to use pooled or individual SDs in tables and figures, when the number of replicates is low. This study uses extensive Monte Carlo simulations (over 2,000 scenarios) to investigate the distributional behaviour of SD estimates across different replications and heterogeneity levels. We compare the performance of pooled versus individual SDs using the Mean Absolute Deviation (MAD) from the true population values, and we evaluate the utility of Levene’s and F max (Hartley’s) tests in guiding this choice. Results show that pooled SDs offer superior accuracy under homogeneity or low heterogeneity conditions, particularly with n  ≤ 4, while individual SDs are preferable when variance heterogeneity is moderate to high and the replication number is higher ( n  ≥ 5). Levene’s test generally outperforms the F max test in supporting the correct selection of the variability measure, especially in multi-group settings. The guidelines proposed can be directly applied to many experimental settings in applied sciences, where the number of replicates and treatments is often limited.

Superheating in mafic magmas controls clinopyroxene nucleation delay and magma ascent dynamics

Abstract Crystallisation kinetics play a fundamental role in controlling conduit dynamics and eruptive style. The degree of superheating is critical in controlling crystallisation kinetics; however, its effect is still debated and has an unclear impact on eruption dynamics. Here, we investigate how superheating influences clinopyroxene nucleation in tephritic magmas from the 2021 Tajogaite eruption (La Palma, Spain) through both in situ and ex situ view experiments. Our findings show that superheating delays nucleation by dissolving pre-existing nuclei, thereby inhibiting crystallisation upon return to subliquidus conditions. Using a numerical model, we investigate how different nucleation delays resulting from different degrees of superheating affect magma ascent dynamics. Depending on the initial thermodynamic conditions and on the pre-eruptive history of magma, an increased nucleation delay can significantly reduce crystal content during ascent, lowering magma viscosity and affecting eruptive style. These findings highlight the critical role of pre-eruptive thermal histories in controlling eruptive style, and provide constraints for refining experimental protocols and numerical models, with direct implications for improving volcanic hazard assessment and eruption forecasting.

Twisted Nanoribbon‐Like Electron Acceptor With Suppressed Non‐Radiative Loss and Seed‐Assisted Crystallization for High‐Efficiency Organic Solar Cells

ABSTRACT While large π‐conjugated nanoribbons possess highly tunable electronic properties, their potential in high‐performance organic photovoltaics (OPVs) remains largely untapped. Herein, we report a π‐extended nanoribbon‐like electron acceptor, PDIY, featuring a molecular length of 4.85 nm (11 fused rings) and near‐infrared absorption extending to 900 nm. PDIY is engineered with a perylene diimide core fused to dual rylene units and end‐capped with Y‐type acceptor moieties. The rigid conjugated framework effectively suppresses conformational/vibronic relaxation, weakens electron‐phonon coupling, and yields an intrinsically low non‐radiative voltage loss (Δ V nr ) of 0.146 eV, among the lowest values reported to date, thereby enabling higher open‐circuit voltage. Despite its large size, the twisted geometry of PDIY leads to a unique “low crystallinity, strong aggregation” behavior. This allows PDIY to serve as a potent morphology‐directing additive that acts in a manner consistent with heterogeneous nucleation, inducing the formation of robust, large‐diameter fibrillar networks within bulk‐heterojunction blends. Consequently, the integration of PDIY yields a simultaneous enhancement across all photovoltaic parameters, boosting power conversion efficiencies (PCEs) from 19.62% to 20.57%. This work establishes twisted nanoribbon‐like acceptor as a versatile molecular platform for the dual regulation of excited‐state dynamics and active‐layer morphology in next‐generation OSCs.

Developing a nomogram based on admission AGR and CLR to predict subsequent surgical intervention in pediatric acute hematogenous osteomyelitis

Abstract Pediatric acute hematogenous osteomyelitis (AHO) can progress rapidly, but admission findings associated with subsequent operative management remain incompletely defined. In this two-center retrospective study, we evaluated the albumin-to-globulin ratio (AGR) and C-reactive protein-to-lymphocyte ratio (CLR) as admission biomarkers associated with surgical intervention during the index hospitalization. Because this outcome is partly clinician-determined, the model was designed to estimate subsequent surgical management rather than the biological necessity for surgery. We included 120 children admitted between 2015 and 2024 (conservative treatment, n = 58; surgical treatment, n = 62). Clinical characteristics, imaging findings, microbiological results, and laboratory variables measured within 2 h of admission and before antibiotic initiation were reviewed. AGR and CLR were modeled as continuous predictors in Firth’s penalized logistic regression and used to construct an admission-based nomogram. Lower AGR and higher CLR were independently associated with surgical intervention (AGR: OR 0.056, 95% CI 0.012–0.220, P  &lt; 0.001; CLR: OR 1.008, 95% CI 1.002–1.018, P  = 0.008). The model showed moderate discrimination (AUC = 0.755; optimism-corrected AUC = 0.749) and satisfactory calibration within this cohort (Hosmer–Lemeshow P  = 0.922; Brier score = 0.198), with internal validation performed using stratified tenfold cross-validation and 1000 bootstrap resamples. At the Youden-derived cutoff of 0.552, sensitivity and specificity were 0.645 and 0.759, respectively. Decision curve analysis suggested potential net benefit mainly across threshold probabilities of approximately 10–60%. These findings indicate that admission AGR and CLR are associated with later clinician-determined surgical intervention and may help identify children who require closer observation, earlier imaging prioritization, and timely reassessment. The nomogram should be considered exploratory and hypothesis-generating; independent external validation is required before routine clinical use.

Automated synthesis of InSb quantum dots with improved batch-to-batch reproducibility via kinetically matched co-reduction

Temperature constrains diet-induced plasticity in the life-history of an aquatic vertebrate

Abstract Temperature is a major force governing ectotherm life-history. To buffer temperature-driven nutritional imbalances, consumers may engage in selective feeding, thereby altering trait expression and life-history configuration as a consequence of trait-specific energetic and nutritional optima. Yet, the joint effects of temperature and diet on life-history architecture remain poorly understood in vertebrate consumers. We reared Bufo spinosus tadpoles under three temperatures (12 °C, 16 °C, 20 °C) and three diet types (animal-based, plant-based, or choice between both), assessing how selective feeding influences trait performance and life-history plasticity. Increasing temperature altered life-history, accelerated larval development and growth, reducing body mass and condition (SMI), with marginal effects on body length. Dietary effects were trait-specific and temperature-dependent, with the animal diet performing better at 12 °C both in growth rate and body mass but losing this advantage at higher temperatures. Tadpoles offered the choice diet fed selectively, leading to lower assimilation of animal-based at higher temperatures, and generally outperformed tadpoles fed fixed diets. However, selective feeding only partially offset the impacts of higher temperatures. Our results show that increasing temperature canalized life-history trajectories, constraining diet-induced plasticity, and highlight the need to integrate thermal and nutritional drivers in predicting ectotherm responses to climate change.

Tailoring electrolyte phase separation for high-rate solid-state lithium metal batteries

Abstract Solid polymer electrolytes are attractive for solid-state lithium metal batteries due to their flexibility and safety but suffer from low ionic conductivity and unstable interfaces. Conventional polymerization-induced phase separation strategies enhance ion transport yet rely on external components such as deep eutectic solvents or ionic liquids, increasing cost and complexity. Here, a LiTFSI-mediated in-situ polymerization strategy is developed to induce controllable phase separation in a poly(vinylene carbonate) matrix using a single solvent. Electrostatic interactions between lithium salts and the polymer drive self-organized dual phases that combine mechanical robustness with efficient ion transport. The resulting PVC electrolyte achieves a tunable ionic conductivity from 0.20 to 0.92 mS/cm at 25 °C and a high lithium-ion transference number of 0.78. Li|PVC-24h | LiFePO 4 cells achieve 121.4 mAh/g at 5 C (12 min) with 90% capacity retention after 4000 cycles, demonstrating a scalable approach for high-performance polymer electrolytes.

Digitizing ESP beyond chalk and talk in the English for tourism classroom

Abstract This study explores faculty members’ perceptions in tourism education programs regarding the use of digital technologies to enhance English language proficiency among learners preparing for careers as tourist guides. The study sample consisted of sixty-five instructors from tourist guide training institutions. Data were collected through semi-structured interviews. The research instrument was developed with reference to English for Specific Purposes (ESP) frameworks to ensure alignment with the linguistic and professional demands of the tourism sector. Data were analyzed using thematic analysis to identify prevailing pedagogical approaches and patterns of technological integration. The findings reveal that faculty members recognized the value of incorporating advanced digital tools, such as simulations, virtual tours, digital assessments, and interactive platforms, into language instruction. These tools were perceived by participants to support learners’ fluency, context-specific vocabulary, self-confidence, and motivation. Moreover, participants perceived the shift to digital methodologies as improving instructional relevance and better aligning educational experiences with industry expectations, potentially increasing students’ preparedness for real-world interactions. The study concludes by emphasizing the need for targeted professional development to equip instructors with the digital competencies required for effective English instruction in tourism contexts.

Design and evolution of the tetracycline repressor into sulfonylurea herbicide-responsive gene switches for field crops

Abstract Chemically inducible expression systems enable transgene expression regulation in response to external small molecules. Tetracycline repressor (TetR)-based gene switches work in plants, but antibiotics are neither approved nor advisable for crop use. Here we report engineering of TetR mutants that respond to approved sulfonylurea (SU) herbicides instead of antibiotics. Designed variants show low-nanomolar EC 50 values for ethametsulfuron-methyl (Es) or chlorsulfuron and tightly bind the Tet operator sequence, but only in the absence of corresponding SUs. Crystal structures of two repressors in complex with their respective SU ligands reveal extensive interactions explaining their strong binding. The Es repressor-based gene switch is introduced into tobacco, soybean, maize, rice, and Arabidopsis , and robust reporter gene activation is observed upon herbicide application. Addition of a repressor-regulated siRNA targeting the repressor transcript increases the magnitude and spatial distribution of the response following herbicide treatment and results in a partially bistable gene switch. The SU repressors also function well in mammalian cell culture and may enable regulation of additional genes in conjunction with TetR.

Bayesian and non-bayesian approaches for estimating the Epanechnikov-Weibull distribution with applications in engineering and electronics data

Abstract Statistical models are widely acknowledged as effective in representing practical scenarios. Nevertheless, it is imperative to recognize that they can sometimes prevent optimal fitting in certain cases. As a result of this awareness, researchers have investigated improved and more efficient probability distributions. This study examines the generalized order statistics (GOSs) of the Epanechnikov-Weibull distribution (EpWD). Statistical features, such as the moment-generating function, the r th L-moment, and trimmed L-moments for this model, are derived. Furthermore, we construct estimation techniques for the model parameters employing maximum likelihood estimation (MLE) and Bayesian approaches. Asymptotic confidence intervals (CIs) are formulated by obtaining explicit formulations for the Fisher information matrix (FIM). A Monte Carlo simulation is conducted to assess the efficacy of the suggested estimators using progressively type-II censored samples. This distribution is also analyzed for its extropy and weighted extropy as information-theoretic measures. The practical applicability of the theoretical findings is illustrated through numerical examples that utilize electronic and engineering datasets.

B-site modulation tailors the size distribution of ex-solved nanoparticles for optimized active sites in perovskites

Monoselective Mechanochemical Aromatic Nucleophilic Substitution Enabled by Crystal‐Engineering‐Guided Reaction Design

ABSTRACT Mechanochemical solid‐state organic transformations using ball milling not only represent a sustainable and efficient synthetic approach but also exhibit reactivity patterns that are remarkably different from conventional solution‐phase reactions. However, the rational design of site‐ and chemoselective synthetic strategies that harness the distinct behavior of solid‐state molecules remains largely unexplored. Here, we present a new reaction based on an organic crystal‐engineering approach to achieve monoselective nucleophilic aromatic substitution (S N Ar) reactions. The mechanochemical solid‐state S N Ar reactions of perfluoroarene derivatives with carbazoles as nucleophiles selectively afforded the monosubstituted products. In contrast, the corresponding solution‐based reactions yielded a mixture of mono‐ and disubstituted products. Single‐crystal X‐ray diffraction analysis of the monosubstituted products revealed strong π–π interactions between the electron‐deficient perfluoroarene moiety and the electron‐rich carbazole unit. These arene–perfluoarene interactions lead to the formation of crystalline solids that are less reactive than the starting materials, thereby suppressing the second substitution and ensuring pronounced monoselectivity. The present study represents a novel approach that leverages a crystal‐engineering principle to design selective solid‐state organic transformations that are difficult to achieve via conventional solution‐based synthesis.

Effects of replacing natural pasture hay with Napier grass on lactation performance and estimated methane emissions in dairy cows

Full-color 3D visualization with Janus metafiber

Bioinspired Starch‐Polyiodide Electrolytes for Self‐Healing Lithium‐Metal Interfaces and Stable Photoelectrochemical Energy Storage

ABSTRACT The development of high‐energy‐density power sources with integrated energy harvesting capabilities is crucial for advancing wearable electronics. Herein, inspired by the homeostatic ion regulation mechanisms of plant roots in dynamic chemical environments, we developed a biomimetic starch‐polyiodide solid polymer electrolyte for constructing an integrated photo‐rechargeable energy storage system. The incorporation of functionalized starch‐polyiodides reconfigures the PVDF matrix topology, modulates the all‐trans (TTTT) conformation and anchors anions, thereby optimizing lithium‐ion transport and enhancing ionic conductivity, while enabling interfacial dead‐lithium self‐healing at the anode and defect passivation of the photoelectrochemical storage cathode (PSC). In situ characterization and theoretical calculations revealed that the additive facilitated multi‐electron transfer and formed a functional buffer layer, which synergistically stabilized the lithium metal anode interface while suppressing ion migration at the PSC. This mechanism established a robust solid electrolyte interphase and improved the overall energy storage efficiency of the integrated device. The resulting flexible integrated device demonstrated outstanding performance, retaining 85% capacity and 95.2% energy efficiency after 450 cycles at 1 C while preserving superior mechanical flexibility and efficient photo‐electric conversion. This work provides a novel strategy for developing flexible energy storage systems that integrate high ionic conductivity, interfacial stability, and photo‐electrochemical synergy.

Energy efficiency of quasi-monochromatic LEDs for road lighting under mesopic vision

Abstract The study addresses the energy efficiency of quasi-monochromatic LEDs for road lighting under mesopic vision conditions. It provides the outcome from the initial stage of research into the potential of such lighting at low adaptation levels. Outdoor electric lighting is widespread and essential for ensuring safety after dark, and current developments increasingly emphasize sustainable LED-based solutions. The existing standards define luminance levels for photopic vision, while nighttime conditions on illuminated roads fall within the mesopic range (0.005–5.000 cd/m 2 ). The research aimed to determine potential of quasi-monochromatic LEDs and energy savings resulting from the use of the light sources in road lighting. Laboratory tests included LED chip samples with peak wavelengths between 495 and 605 nm. The analysis considered the spectral power distribution, S/P ratio and mesopic luminous efficacy of the LEDs, normalized power density and annual energy density for road lighting under mesopic vision conditions. The results confirmed that quasi-monochromatic LEDs are an alternative worth studying for mesopic vision conditions and can improve the energy efficiency of road lighting. For LEDs emitting within 495–570 nm range, mesopic luminous efficacy increased as adaptation luminance decreased. The analysis also showed that, compared with HPS lamps, a 570 nm LED and a mixed spectrum combining 2884 K and 500 nm LEDs may offer up to 20% higher energy efficiency at the lowest lighting levels (0.3–0.5 cd/m 2 ). Consequently, annual energy savings in road lighting may reach approximately 20% relative to HPS lamps and even 30% relative to a typical white LED.

Encoding orbital angular momentum of light in space with optical catastrophes

Abstract Light beams carrying orbital angular momentum (OAM) possess an unbounded set of orthogonal modes, offering significant potential for optical communication and security. However, exploiting OAM beams in space has been hindered by the lack of a versatile design toolkit. Here, we demonstrate a strategy to tailor OAM across multiple transverse planes by shaping optical caustics leveraging on catastrophe theory. With 3D-printed metasurfaces fabricated using two-photon polymerization lithography, we construct these caustics to steer Poynting vectors and achieve arbitrary shapes of OAM beams. Interestingly, we further realize “hidden” OAM along the propagation trajectory, where the intensity of the beam is spread out thus avoiding detection. By exploiting this intrinsic nature of OAM, we demonstrate the detection of encoded information in optical encryption. Our approach provides a unique framework for dynamic control of OAM in space, with promising applications in optical trapping and sensing, high-capacity data storage, and optical information security.

A Cu–La Dual‐Atomic Catalyst With Dual‐Site Adsorption Enables Synergistic Optimization of Thermodynamics and Kinetics of Electrocatalytic CO ₂ Reduction

ABSTRACT Single‐atomic catalysts face the following major challenges in the rapidly advancing field of electrocatalytic CO 2 reduction (ECR) to CO: linear scaling relationships between adsorption strengths of intermediates lead to unfavored ECR thermodynamics; low CO 2 /proton/electron concentrations within microenvironments on catalyst surfaces limit ECR kinetics. Consequently, we synthesized a Cu–La dual‐atomic catalyst (DAC) for synergistically optimizing the ECR thermodynamics and kinetics. The Cu and La sites of Cu–La DAC can respectively couple the C and O atoms of *COOH, forming a novel dual‐site *COOH adsorption configuration, which does not undergo a transition to subsequent *CO. Cu–La DAC can effectively break the linear scaling relationship and optimize the ECR thermodynamics. Furthermore, Cu and La, possessing distinct conductivity, hydrophilicity, and CO 2 adsorption capabilities, collectively modulate the microenvironments on the surface of Cu–La DAC. This facilitates the efficient supply of electrons, protons, and CO 2 for ECR, thereby greatly enhancing the kinetics. This work combines Cu and La, which have different macroscopic properties and electronic structures (microscopic), to synergistically optimize thermodynamics and kinetics based on the dual‐site adsorption of DAC, providing new insights for designing high‐performance catalysts and discovering efficient mechanisms.