Browse Articles

Synergizing Mass Transfer and Exciton Dissociation in Nanoscale COFs for Efficient H ₂ O ₂ Photosynthesis

ABSTRACT Covalent organic frameworks (COFs) are promising photocatalysts for solar H 2 O 2 production, but their efficiencies remain insufficient for practical application. A primary limitation stems from the coupled proton–electron transfer in the two‐electron oxygen reduction reaction (2e − ORR), which demands photoinduced charge generation and rapid proton delivery—features rarely optimized simultaneously in existing COF architectures. Here we address these bottlenecks by combining nanoscale morphological control with pore‐wall functionalization. Bottom‐up colloidal synthesis produces highly crystalline COF nanospheres that reduce exciton‐diffusion losses and enhance light harvesting and charge generation versus bulk COFs. Meanwhile, carboxylic acid groups incorporated into 1D nanopores tune the microenvironment to promote proton delivery. This unified design delivers an exceptional H 2 O 2 evolution rate of 11246 µmol g −1  h −1 (>sevenfold enhancement over pristine bulk COF), and a solar‐to‐chemical conversion efficiency of 2.18% in pure water under air (AM 1.5G, 100 mW cm −2 ), among the highest reported for COF‐based photocatalysts. Experimental investigations and theoretical calculations reveal the carboxylated pore walls template continuous, oriented hydrogen‐bond chains in confined water, lowering the kinetic barrier for the 2e − ORR pathway. This work establishes a generalizable paradigm for orchestrating coupled proton–electron transfer in porous photocatalysts for efficient solar energy conversion.

Hydrogen sulfide inhalation induces changes in body physiology and lung gene expression in mice

Correction: Development and testing of a composite index to monitor the continuum of maternal health service delivery at provincial and district level in South Africa

Breaking the Fixed Output: Harnessing Photonic Reabsorption and Photothermal Effects for Tunable NIR Waveguiding in a Flexible Organic Crystal

ABSTRACT Flexible organic crystals have emerged as promising materials for integrated photonic devices and optical communication systems. However, the output wavelength and intensity of optical signals are typically fixed by the intrinsic molecular structures and crystal packing modes, rendering continuous and reversible modulation of a sole crystal highly challenging. Herein, we design and synthesize a near‐infrared flexible organic crystal, in which dual‐mode waveguide output modulation of wavelength and intensity is achieved by synergistically exploiting photonic re‐absorption and photothermal‐driven fluorescence deactivation. Owing to the pronounced overlap between the absorption and emission spectra, the waveguide output wavelength of the crystal can be continuously tuned from 730 to 824 nm based on the light propagation distance. Meanwhile, the crystal exhibits rapid, stable, and highly reversible photothermal conversion under 660 nm laser irradiation. Coupled with temperature‐dependent fluorescence deactivation, this photothermal effect enables remote modulation of waveguide output intensity by simply adjusting the irradiation power of the input laser. This work establishes a non‐contact, structure‐preserving strategy for overall modulation of optical waveguides, providing new opportunities for the development of flexible near‐infrared photonic devices and reconfigurable optical systems.

Valorization of teak wood biomass into nanobiochar for environmental remediation

Acute effects of three warm-up protocols on drop jump biomechanics in elite Taekwondo athletes: An IMU-based analysis

This randomized, parallel-group pre–post study examined the acute effects of three warm-up modalities on stretch–shortening cycle (SSC) biomechanics in elite female Taekwondo athletes. Thirty-six participants were randomly assigned to dynamic stretching, foam rolling, or resistance-band (TheraBand) protocols following a standardized submaximal treadmill warm-up. Three-dimensional kinetic and temporal variables were collected during drop jump tasks before and after each intervention using inertial measurement units.Between-group post-intervention differences were analyzed using analysis of covariance (ANCOVA) or rank-based Quade’s ANCOVA, controlling for baseline disparities. Within-group changes were assessed using paired parametric or non-parametric tests as appropriate. Effect sizes (η²) are reported alongside p-values to indicate the magnitude of observed effects.Significant group effects were observed for concentric phase duration (η² = 0.177), peak concentric force (η² = 0.186), and mean concentric power (η² = 0.211). Post-hoc analyses revealed that dynamic stretching enhanced concentric force and power, while foam rolling primarily altered temporal characteristics of force development. TheraBand preserved performance close to baseline. In contrast, gross performance outcomes such as jump height, flight time, and contact time showed trivial effect sizes (η² ≤ 0.104) and no significant between-group differences. These findings indicate that warm-up modalities selectively modulate force- and power-related components of SSC function rather than uniformly enhancing overall jump performance. By ‘selective modulation,’ we mean that different warm-up protocols influence distinct components of stretch-shortening cycle function rather than producing a generalized enhancement. Specifically, dynamic stretching primarily improved concentric force and power output; foam rolling altered temporal characteristics (e.g., concentric duration and time to peak power) without increasing peak force; and TheraBand preserved baseline performance across most variables. This selective response indicates that warm-up modality should be matched to the specific neuromuscular demand of the subsequent task. Post-hoc comparisons clarify which groups differ, highlighting the practical utility of dynamic stretching for enhancing propulsive-phase mechanics in elite athletes.

Selective Two‐Electron Phenol Oxidation Polymerization for Water Purification

ABSTRACT Highly reactive phenoxonium ion (PhO + ), generated via two‐electron oxidation, exhibits remarkable efficacy in polymerizing and removing phenolic contaminants. However, the sequential two‐electron abstraction from phenol to form PhO + remains a significant kinetic and thermodynamic challenge. Herein, we report an N‐bridged double‐iron site (≡Fe─N─Fe ≡) catalyst that enables PhO + generation through peroxymonosulfate (PMS) activation. In situ spectroscopy and theoretical calculations reveal that PMS adsorbs onto the ≡Fe─N─Fe ≡ site via both peroxide oxygen atoms (─O─O─), forming a ≡Fe‐(μO─O)─Fe≡ intermediate. This unique structure provides dual low‐lying Fe─O σ*(‐ p z ) orbitals, and minimizes the energy gap between the Fe orbital and the O─O σ* orbital, thereby catalyzing two‐step single‐electron transfer from phenol to the ─O─O─ and enabling the PhO + formation. This PhO + ‐induced C─O coupling polymerization achieves an 81.8% polymerization transfer ratio, significantly higher than that obtained via the phenoxy radical (PhO•)‐mediated process (35.0%). This system enables the rapid phenol removal (98.1% in 3 min) and the effective treatment of coking wastewater, maintaining > 97% phenol removal over 10 d in a continuous‐flow reactor. Our work provides an atomic‐level design principle for steering oxidation pathways, opening a sustainable route for water purification that simultaneously eliminates pollutants and recovers carbon resources.

Solvent‐Gated Multimodal Charge Transfer Interactions for Precise Supramolecular Chirality Control

ABSTRACT Despite the widespread application of charge transfer (CT) interactions in chiral optoelectronic materials, achieving multimodal CT interactions for the precise control poses significant challenges in both molecular design and practical implementation. Here, we develop amino acid‐based folded structures integrating pyrene donors and aryl imide acceptors with sterically hindering tert‐butyl groups, which exhibit dynamic through‐space CT interactions in solutions, enabled by reversible solvent‐gated folding/unfolding. The conformational switching induces distinct responses, enabling tunable emission spanning from blue to yellow to achieve white‐light emission, alongside precise regulation of chiroptical properties. Apart from solution‐based CT complexation, robust CT complexes with excellent chiroptical properties form within polymer matrices. Bottom‐up self‐assembly also leads to amplified chiroptical signals and the generation of macroscopic chirality. Remarkably, solvent ratio controls hierarchical self‐assembly via alternate or segregated CT stacking modes, generating helical aggregates with Inverted handedness, and simultaneously inducing macroscopic supramolecular chirality and enhanced chiroptical signals. Thermodynamically driven supramolecular chiral‐selective ripening inverts the initial kinetically trapped chirality, leveraging the stability of alternating CT stacks to achieve homochirality. This architecture exhibits remarkable solvent‐controlled modulation of luminescence, chiroptical handedness, and supramolecular chirality, offering a versatile platform for advanced photonics and multimodal encryption.

Bidirectional cross-modal fusion with tensor interaction for drug-target binding prediction

China runoff-field forecasting based on cross-scale gating and basin-topology attention

Accurate multi-step runoff forecasting over China is important for flood control, water-resource management, and regional hydrological assessment. However, existing data-driven methods often struggle to jointly capture temporal variations at different time scales and the directional hydrological dependencies imposed by river networks, which limits forecasting accuracy and spatial structural consistency. To address this issue, this paper proposes a spatiotemporal forecasting framework that combines cross-scale temporal fusion with basin-topology-guided spatial modeling. Specifically, a multi-scale temporal module with cross-scale gating is introduced to adaptively integrate short-, medium-, and long-term runoff variations, while a basin-topology attention module incorporates upstream–downstream connectivity into spatial dependency learning. Experiments are conducted on a China-scale gridded runoff forecasting benchmark derived from the publicly available GloFAS Historical dataset through spatial filtering, valid-region masking, and forecasting-oriented sample construction. The proposed method achieves better overall performance than representative baselines in terms of MAE, RMSE, PSNR, and SSIM. In the overall comparison, it reaches MAE 0.0269 and RMSE 0.0603 in normalized log-scale runoff units, PSNR 24.39, and SSIM 0.9273, while maintaining a moderate parameter size and practical inference efficiency. The results demonstrate that the proposed framework reduces numerical errors and better preserves the spatial patterns of runoff fields. Ablation studies further confirm that both cross-scale gating and basin-topology attention contribute consistently to the overall improvement.

Electron‐Isolating Band Solidified Fe─O Bond in Ni/NiFe Layered Double Hydroxide Composite for Stable Ampere‐Level Simulated Seawater Oxidation

ABSTRACT The dissolution of iron ions triggers irreversible structural collapse and resultant catastrophic deactivation in NiFe‐layered double hydroxides (NiFe LDHs), representing a formidable challenge to their implementation in sustainable hydrogen production. Herein, by adjusting the Ni nanoparticle content in Ni/NiFe LDH composites synthesized via reduction–coprecipitation method, Fe t 2g orbital occupancy is regulated to protect the Fe─O bond from cleavage. Specifically, with considerable electron transfer from Ni to Fe t 2g orbital, the low‐energy antibonding of Fe t 2g * band separates from the (Fe─O) bonding band, lying near and crossing the Fermi level, as evidenced by x‐ray absorption spectra (XAS) and the calculated density of states. This band serves as an electron‐isolating band to avoid electron removal from the (Fe─O) bonding band, which significantly solidifies the Fe─O bond confirmed by operando XAS. Additionally, the modulation lowers the adsorption energy of Cl − , suppressing the chloride‐induced electrocatalyst corrosion in seawater electrolysis. Consequently, the optimal sample operates stably at 1 A cm −2 for over 10 000 h in the three‐electrode system and beyond 450 h in an anion‐exchange membrane water electrolyzer under simulated seawater oxidation, ranking among the state‐of‐the‐art powder‐type NiFe LDH‐based catalysts. This work highlights the manipulation of antibonding orbital state for fundamentally enhancing electrocatalyst stability.

Breaking Electronic Insulation of Monocyclic Aromatic Spacers via Hydrazide‐Induced Orbital Coupling in Ruddlesden‐Popper Perovskites

ABSTRACT Ruddlesden–Popper perovskites are promising photovoltaic materials because their enhanced structural and environmental stability relative to their three‐dimensional counterparts. However, weak interactions between organic spacer and the adjacent inorganic framework often undermine structural stability and impede charge transport. Here, we demonstrate that the hydrazide‐based spacer, thiophene‐2‐hydrazide (ThCH), unexpectedly induces strong interlayer orbital coupling in 2D RP perovskites despite its monocyclic aromatic structure. It is found that the hydrazide group extends electronic conjugation and promotes orbital hybridization between ThCH and the adjacent inorganic framework, a phenomenon not observed in conventional single‐ring aromatic spacers. This effect is further verified by benzo hydrazide, which shares a similar structural motif. Beyond promoting electronic coupling, the hydrazide functionality enhances film formation, yielding enhanced crystallization uniformity and facilitating efficient charge transport. Consequently, ThCH‐based RP perovskite (nominal n = 4) devices achieve record efficiencies of 22.41% (certified 21.74%, 0.074 cm 2 ) for small‐area devices and 20.74% (certified 20.01%, 1.015 cm 2 ) for large‐area devices, the highest reported for quasi‐2D RP PSCs. This study establishes a molecular design strategy that uses multifunctional hydrazide modules to overcome the electronic insulation of single‐ring aromatic spacers, enabling robust and efficient RP PSCs.

A method for tissue-mask supported whole-body image registration in the UK Biobank

Abstract The UK Biobank is a large-scale study collecting whole-body MR imaging and non-imaging health data. Robust and accurate inter-subject image registration of these whole-body MR images would enable their body-wide spatial standardization, and region-/voxel-wise correlation analysis of non-imaging data with image-derived parameters (e.g., tissue volume or fat content). We propose a sex-stratified inter-subject whole-body MR image registration approach that uses subcutaneous adipose tissue- and muscle-masks from the state-of-the-art VIBESegmentator method to augment intensity-based graph-cut registration. The proposed method (that we refer to as mask-supported ) was evaluated on a subset of 4000 subjects by comparing it to an intensity-only method as well as two previously published registration methods, uniGradICON and MIRTK. The evaluation consisted of a comparison of Jacobian Determinant (JD) folding frequency, Dice scores, and voxel-wise label error frequency calculated from the 71 VIBESegmentator masks. The 40 masks from MRSegmentator and 50 masks from TotalSegmentator were also used for independent Dice score evaluations. Additionally, voxel-wise correlation between age and each of fat content and tissue volume was studied to exemplify the usefulness for medical research. The proposed method showed 7percentage points (pp) / 11pp lower frequency of JD folding for males / females when compared to the intensity-based method. The mask-supported method exhibited a mean Dice score of 0.773 / 0.744 across the cohort when evaluated on all VIBESegmentator masks, excluding the two used in the registration, for males / females, respectively. In comparison to the intensity-only registration, the mean values were 6 pp higher for both sexes, and the label error frequency was decreased in most tissue regions. These differences were 9pp / 8pp against uniGradICON and 12pp / 13pp against MIRTK. The mask-supported method achieved a mean Dice score of 0.736 / 0.676 when evaluated with MRSegmentator and 0.683/ 0.617 when evaluated with TotalSegmentator, showing an increase that ranged between 0.7pp and 12pp from the other three methods. Using the proposed method, the age-correlation maps were less noisy and showed higher anatomical alignment. In conclusion, the image registration method using two tissue masks improves whole-body registration of UK Biobank images.

Comparative modeling of mixed cardiopulmonary sounds in a low-resource paired dataset: Discrimination, calibration, and operating-point behavior

Background Mixed cardiopulmonary recordings are common in bedside auscultation, yet most automated systems have been developed for isolated heart sounds or isolated respiratory sounds. Methods We conducted a comparative methods study on HLS-CMDS, a low-resource paired dataset containing mixed recordings with matched isolated heart and lung source recordings. The task was dual binary classification from a single mixed recording. We compared feature-based references, a shared-backbone multitask CNN, a target-domain student model, teacher-guided variants pretrained on PhysioNet/CinC 2016 and ICBHI 2017, and lighter source-aware variants using paired HLS-CMDS source recordings. A nested grouped five-fold evaluation was performed at the triplet level; within each outer training fold, an inner validation split was used for checkpoint selection, temperature scaling, and task-specific threshold selection. Results Under the revised nested evaluation, the light source-aware model showed the strongest mean discrimination (macro AUROC 0.7107 ± 0.1659; macro AUPRC 0.9318 ± 0.0423). The prevalence-defined no-skill macro AUPRC baseline was 0.8586 ± 0.0225. After inner-validation temperature scaling and threshold selection, the calibrated student-only model achieved the highest mean macro balanced accuracy (0.6894 ± 0.0548). The observed differences were interpreted cautiously because fold-to-fold variability was substantial. Conclusions In this small paired mixed-sound setting, restrained source-aware guidance showed the strongest discrimination tendency, whereas a simpler target-domain model achieved the best threshold-dependent balanced accuracy after calibration.

Molecular Engineering of Vibronic Coupling Enables High‐Temperature Solar–Thermal Conversion in an Organic Material

ABSTRACT Solar–thermal conversion offers a direct route for harvesting solar energy, yet most organic materials reported are limited to moderate temperatures and low‐temperature applications. Here, we report BTDyA, an organic material designed for high‐temperature solar–thermal conversion, achieved by bridging triphenylamine donors with [1,2,5]thiadiazolo[3,4‐f]benzotriazole acceptor via ethynyl linkages. BTDyA demonstrates a high molar absorption coefficient and broadband solid‐state absorption, enabled it to reach a temperature as high as 330 °C under concentrated outdoor sunlight, the highest reported value for organic solar–thermal materials. Moreover, under 1064 nm laser irradiation, the temperature could be further elevated to 377 °C. The transient absorption and photoinduced Raman spectroscopies reveal that BTDyA undergoes ultrafast nonradiative decay in the excited‐state, coupled with significant vibronic activation. These promote efficient conversion of photon energy into molecular vibronic energy and heat, while suppressing radiative losses and enhancing photothermal performance. The high‐temperature capability of BTDyA positions it as a promising candidate for solar energy harvesting and thermal storage. These findings offer critical insights into the design principles and photothermal mechanisms of organic materials for high‐temperature solar–thermal applications, paving the way for their future use in renewable energy technologies.

Engineering of Donor‐Acceptor Nanodomains in Zn‐Salen COFs Enhances Efficient Coupling Photoredox of Oxygen and Indoline

ABSTRACT The photocatalytic coupling of molecular oxygen with organic substrates, such as indoline represents a sustainable solar‐to‐chemical strategy. However, designing highly‐efficient organic photocatalysts still remains a significant challenge. Herein, three Zn‐Salen covalent organic frameworks (COFs, Zn‐Salen‐EN, ‐PD, and ‐HATP) with tunable donor‐acceptor (D‐A) nanodomains were synthesized through combining the same Zn‐Salen acceptor units with different electron‐donating linkers including ethylenediamine (EN), 1,2‐phenylenediamine (PD), and 2,3,6,7,10,11‐hexaaminotriphenylene (HATP). Among them, Zn‐Salen‐PD exhibits best activity for the two‐electron photoreduction of O 2 (2e − ORR) to produce hydrogen peroxide (H 2 O 2 ) with a rate of 26 700 µmol g cat −1 h −1 , while simultaneously enabling efficient photocatalytic indoline dehydrogenation to generate indole (2e − IND‐DR). The enhanced performance of Zn‐Salen‐PD stems from its optimal D‐A spatial alignment and a tailored band structure, which achieve a balanced synergy among exciton dissociation, charge carrier lifetime, and electron reduction capability. Moreover, mechanistic insights from in situ spectroscopy and theoretical calculations revealed that ZnN 2 O 2 motifs served as efficient Griffith‐type 2e − ORR active centers, while photoinduced holes accumulated on the donor units to drive 2e − IND‐DR. This work demonstrates that the nanoscale engineering of D‐A structures within metal‐COFs offers a powerful strategy for enabling coupled photoredox transformations.

Retraction Note: Flavokawain C suppresses nephroblastoma growth by inducing autophagy-mediated downregulation of FABP4 via AMPK/mTOR pathway

Reappraisal of a historical porfimer sodium photodynamic therapy study for vascular restenosis: Efficacy, high procedural mortality, and methodological insights from a rabbit balloon-injury model

Background Restenosis driven by intimal hyperplasia remains a major limitation of peripheral arterial intervention. Photodynamic therapy (PDT) using porfimer sodium (Photofrin®) demonstrated promising preclinical efficacy in the 1990s; however, its translation into clinical vascular practice has been stalled. We reappraised a historical pilot dataset to evaluate both biological efficacy and procedural feasibility. Methods In a rabbit model of bilateral femoral artery balloon injury (10 animals initiated), one artery per animal received intraluminal PDT (630 nm, ~ 5.6 J/cm²) 48 h after intramuscular porfimer sodium administration (2 mg/kg), while the contralateral artery served as an internal control. Histomorphometric analysis of the intima-media ratio (IMR) was performed 21 days after injury. Results The procedural feasibility of this approach is severely limited. Only three of the ten animals yielded analyzable paired arterial samples because of high intraoperative mortality (40%) and postoperative complications. In surviving animals, PDT-treated arteries demonstrated a consistent and marked suppression of neointimal hyperplasia compared with controls (IMR 0.29 ± 0.07 vs. 1.65 ± 0.55; P < 0.001 ), corresponding to a median IMR reduction of 82%. Conclusions This reappraisal confirms the potent biological effects of porfimer sodium-mediated PDT on neointimal hyperplasia. However, the principal contribution of this study lies in the transparent documentation of critical translational barriers, particularly the unsustainable procedural mortality associated with this model of bilateral injury. By providing detailed dosimetry parameters and a candid feasibility analysis, this study offers methodological insights to guide the design of safer and more translatable preclinical vascular PDT studies in the future.

Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal

ABSTRACT Developing birefringent materials that simultaneously exhibit short ultraviolet (UV) cutoff edges and large birefringence is highly desirable but remains challenging. Here, we report a peroxide‐containing solvate crystal, 4HP ·H 2 O 2 ( 4HPO2 , 4HP = 4‐hydroxypyridine), obtained by incorporating H 2 O 2 into the 4HP lattice through a mild aqueous‐solution method. 4HPO2 exhibits a solar‐blind UV cutoff edge at 278 nm together with a giant experimental birefringence of 0.609@546 nm, representing an approximately 14‐fold enhancement compared with pristine 4HP . Structural analysis reveals that H 2 O 2 induces a pronounced reorganization of the 4HP packing, converting a nearly orthogonal arrangement into an ordered, nearly parallel alignment through strengthened hydrogen‐bonding interactions. Combined experimental and theoretical analyses indicate that the aligned 4HP sublattice serves as the dominant source of optical anisotropy, whereas H 2 O 2 mainly acts as a hydrogen‐bond‐directed structural modulator with a secondary direct optical contribution. The reordered packing also creates an anisotropic local‐field environment that further amplifies the molecular polarizability anisotropy ( Δα ). These findings highlight peroxide‐assisted solvate engineering as an effective strategy for tuning packing and optical anisotropy and provide a promising design principle for developing ultraviolet birefringent materials.

Tailoring Intermolecular Chemistry and Interphases via F, N‐Functionalized Polymer Matrix in High‐Flash‐Point Ether‐Ester Hybrid Electrolytes for Intrinsically Safe Quasi‐Solid‐State Li Metal Batteries

ABSTRACT In situ polymerized quasi‐solid‐state electrolytes (QSEs) are promising for lithium metal batteries (LMBs) yet face challenges regarding high‐voltage stability and kinetics. Herein, a novel ether‐ester hybrid QSE is achieved through the in situ copolymerization of 2,2,2‐trifluoroethyl acrylate (TFEA) and 2‐isocyanatoethyl methacrylate (IEM) within a tetraethylene glycol dimethyl ether (G4)/fluoroethylene carbonate (FEC) solvent system. This design leverages synergistic interactions between the functionalized polymer matrix (─CF 3 and ─N═C═O) and liquid components. The incorporation of FEC and the regulatory effect of the polymer backbone tailor the Li + solvation structure toward an anion‐rich configuration, which gives rise to a robust, antioxidative, and inorganic‐rich interphase. Furthermore, hydrogen bonding interactions effectively immobilize PF 6 − anions and free G4 molecules, thereby elevating the Li + transference number and enabling the electrochemical stability window over 4.8 V (vs. Li + /Li). The QSE exhibited a high room‐temperature ionic conductivity of 2.2 × 10 −3 S cm −1 . Consequently, 4.2 V Li|| LiFePO 4 (LFP) cells demonstrate 93% capacity retention over 1,000 cycles, while 4.5 V Li||NCM811 (NCM811) cells retain 80% over 300 cycles. A specific energy of 302.64 Wh kg −1 is attained in a 2 Ah Li||NCM811 pouch‐type cell. These findings highlight tailored molecular design and controlled interactions as a viable route for advancing high‐energy‐density quasi‐solid‐state batteries.