Browse Articles

Intermolecular Interactions Regulating Exciton Behavior in Hydrogen‐Bonded Organic Framework for Photocatalytic Aerobic Oxidation

ABSTRACT Exciton effects play a vital role in photocatalytic reactions, yet their precise regulation remains highly challenging, as even subtle variations can lead to pronounced differences in exciton behavior. To date, the influence of intermolecular interactions on exciton dynamics remains largely unexplored. Herein, two isoreticular donor‐acceptor hydrogen‐bonded or ganic frameworks (D–A HOFs), PFC‐19 and PFC‐70, are synthesized. Notably, PFC‐70's monomer lacks an intrinsic donor‐acceptor structure. However, pronounced orbital perturbation and reorganization occur during its self‐assembly, leading to an emergent D–A reconstruction. In contrast, PFC‐19 retains orbital distribution similar to its monomer. These distinct behaviors originate from stronger intermolecular interactions in PFC‐70, thereby inducing dramatic energy‐level reorganization. Consequently, PFC‐19 predominantly generates 1 O 2 via an energy‐transfer pathway. On the contrary, PFC‐70 shows a reduced exciton binding energy and enhanced charge‐transfer efficiency, leading to the formation of O 2 • − /•OH via a charge‐transfer‐dominated process. Accordingly, photocatalytic aerobic organic transformations are achieved, exhibiting excellent efficiency in 1 O 2 ‐mediated C‐3 arylation of quinoxalin‐2(1 H )‐ones with PFC‐19 and predominant O 2 • − ‐triggered oxidative coupling of benzylamines over PFC‐70. This work not only provides a general strategy for regulating intermolecular interactions via molecular engineering but also gains deep insight into exciton regulation for controlling ROS species in noncovalently assembled systems.

Examining urban heat island progression in Chennai: temporal insights from 2014 to 2024

Zexin Jin

Latent profiles of actual and perceived motor competence are associated with physical activity and BMI in childhood: a latent profile analysis

Cascade Reaction for Efficient ¹ O ₂ Generation Enabled by Spatially Coupled Vacancy Pairs

ABSTRACT Singlet oxygen ( 1 O 2 ) is a powerful nonradical oxidant for water purification, particularly in complex matrices. However, its spin‐forbidden generation from triplet oxygen ( 3 O 2 ) imposes significant thermodynamic barriers. This study reports a pulsed‐laser synthesis strategy to create atomically adjacent vacancy pairs (V Ti–O ) on the surface of TiO 2 , which function as a cooperative bifunctional redox nanoreactor for the sustainable generation of 1 O 2 . The oxygen vacancy (V O ) serves as a reduction site for O 2 adsorption and activation, whereas the adjacent titanium vacancy (V Ti ), acting as an oxidation site, immediately converts superoxide (O 2 ·− ) into 1 O 2 . The V Ti–O pair shortens the migration path of O 2 ·− , inhibits quenching, and enhances the overall reaction kinetics. In an integrated fixed‐bed reactor operated under natural sunlight in a real water environment, this catalyst enables efficient pollutant degradation while maintaining aquatic biocompatibility, demonstrating its practical potential for low‐energy, efficient 1 O 2 generation and wastewater treatment in sustainable solar‐driven advanced oxidation processes.

Health literacy and environmental health behaviors in the context of microplastic exposure: a cross-sectional study in rural Thailand

Abstract Microplastic contamination has emerged as a growing environmental exposure concern in river-dependent rural populations, yet evidence on behavioral determinants remains limited. Health literacy is a key upstream determinant that may influence risk perception and preventive behavioral responses. This study examined the association between health literacy and preventive behaviors related to microplastic exposure among residents living along the Mun River in Buriram Province, Thailand. A community-based cross-sectional study was conducted among 268 adults selected using multistage sampling. Data were collected through structured interviewer-administered questionnaires. Health literacy was operationalized as a multidimensional construct covering six domains and categorized into sufficient and insufficient levels. Preventive behaviors were dichotomized as good or poor based on predefined scoring criteria. Multivariable logistic regression models were applied to estimate adjusted associations between health literacy and preventive behaviors while controlling for potential confounders, including sociodemographic and behavioral factors. Adjusted odds ratios (AORs) with 95% confidence intervals (CIs) were reported. Insufficient health literacy was highly prevalent (70.9%) and was independently associated with poor preventive behaviors (AOR = 6.05, 95% CI: 3.08–11.90, p  < 0.001) after adjustment for covariates. Domain-specific analysis identified action literacy (AOR = 2.67, 95% CI: 1.29–5.59, p  = 0.008) and appraisal literacy (AOR = 3.19, 95% CI: 1.51–6.73, p  = 0.002) as significant predictors. Frequent fish consumption was also independently associated with poor preventive behaviors (AOR = 3.25, 95% CI: 1.35–7.84, p  = 0.009). Health literacy is a strong independent correlate of preventive behaviors related to microplastic exposure in rural riverine populations. Findings support targeted, domain-specific health literacy interventions—particularly action- and appraisal-oriented competencies—as a public health strategy to reduce environmental exposure risk.

Total Synthesis of Allocyclinone A via Late‐Stage Halogen Swapping

ABSTRACT Allocyclinones A–D are small congeners of angucyclinones with several unusual structural features and potent antibiotic activity against various Gram‐positive pathogens. Allocyclinone A, the most active congener, contains an intriguing aromatic trichloromethyl substituent that has never been observed in other natural products before. In this study, we report a modular total synthesis of allocyclinones A and B featuring the convergent assembly of three key building blocks through Hauser annulation and cross‐couplings. The synthesis of allocyclinone A was made possible by the application of a late‐stage trifluoromethyl‐to‐trichloromethyl swap, providing a potentially generalizable strategy for aromatic trichloromethyl installation in complex settings. The antibiotic activity of the scaffold was also verified, and attempts to elucidate its mode of action were performed.

Assessment of anti-VEGF intravitreal injection effects on murine neonatal Schlemm’s canal morphology

Dual‐Channel Interdigitated Aptamer‐Based Sensors for Rapid Small‐Molecule Detection in Biofluids

ABSTRACT Timely and decentralized quantification of small‐molecule biomarkers is essential for point‐of‐care (POC) diagnostics, but their reliable detection in biofluids remains challenging. Here, we introduce an engineered electrochemical aptamer sensing platform that employs a dual‐channel signal conversion strategy to overcome these limitations. By integrating spatially separated interdigitated working electrodes with selective self‐assembled monolayer (SAM) removal, the system enables target‐induced release and recapture of methylene blue‐labeled complementary DNA (MB‐cDNA) probes across two electrodes. This configuration minimizes background interference and enhances mass transport, facilitating robust dual‐channel signal transduction. The platform enables rapid (≤ 30 min), low‐volume (30 µL) detection of prototypical small molecules, dopamine and cortisol, in diverse biofluids, including artificial cerebrospinal fluid (aCSF), human serum, and saliva. Notably, the signal conversion mechanism remained effective across different targets and sample types, requiring only minimal adaptation of the recognition sequence. Together, these features establish a versatile electrochemical sensing architecture with broad potential for rapid, quantitative small‐molecule analysis in complex biological media.

Chaos-driven design of highly nonlinear S-boxes for secure and efficient lightweight image encryption

Visible‐Light Unlocked Carbene Insertion and Radical Release in a Structurally Constrained Pincer Phosphorus Compound

ABSTRACT Geometrically constrained phosphines have attracted significant attention for their ability to mediate reactions traditionally associated with transition metals. Here, we show that visible‐light excitation unlocks new transition‐metal‐like reactivity in a well‐studied ONO‐pincer phosphine. Photochemical generation of α‐siloxy carbenes enables rapid P─C bond formation, affording bicyclic phosphines with complete diastereocontrol. These phosphine intermediates readily engage with electrophiles to form air‐ and moisture‐stable phosphoranes, which, upon subsequent irradiation, undergo selective P─C bond homolysis, releasing carbon‐centered radicals while regenerating the initial phosphine framework. Time‐resolved EPR spectroscopy and DFT calculations reveal that geometric constraint is crucial for accessing both carbene‐insertion rearrangement and P─C bond homolysis pathways not observed with conventional phosphines. Together, these findings establish a rare light‐driven phosphine → phosphorane →phosphine (P(III) → P(V) → P(III)) reactivity loop and demonstrate how structural constraint enables main‐group centers to perform elementary steps analogous to transition metals.

Influence of high-fat diet and sex on connective tissue in carpal tunnel syndrome

Dispersal mode and spatial heterogeneity shape the interaction between adaptation and dispersal in multitrophic metacommunities

The Role of Shape Commensurability in Chirality Transfer: Gold Nanoshape Solutes in a Discotic Nematic Liquid Crystal Solvent

ABSTRACT Chirality, as an inherently geometric concept, is well understood at most length scales and is a principal attribute of objects and figures. Quantitative models predicting the efficacy of chirality transmission across length scales have only recently begun to emerge. We provide further proof‐of‐concept data and calculations for a modus operandi for nanoshape solutes featuring a chiral ligand shell in an achiral discotic nematic (ND) liquid crystal solvent, demonstrating that chirality transfer can be understood through remarkably simple geometric considerations. This mechanism is based on the product of a pseudoscalar chirality indicator and a geometric shape compatibility factor based on the 2D isoperimetric quotients for nanoshape solutes and N D molecule. The model is tested on an experimental set of precisely engineered gold nanoshapes, rods, prisms, and discs, that validates that shape commensurability between nanoscale solute and nematic solvent is a prerequisite for efficacious chirality transfer as determined by the helical twisting power of the nanoshapes in the induced chiral N D * phase. Thus, we predict that libraries of calculated and in‐parallel acquired experimental data among related nanoshapes and even small organic molecules pave the way for predictive calculations of chirality transfer in nanoscale, macromolecular, biological, and small‐molecule systems.

Evolution of network structure and driving mechanisms of food production resilience in arid regions: a machine learning-based approach

Synergistic Lewis Acid Photocatalysis Over Cluster‐Defect‐Engineered UiO‐66 for Efficient Liquid Biomass Upgrading

ABSTRACT Defect engineering provides new opportunities to overcome the intrinsic limitations of metal–organic frameworks (MOFs) in photocatalysis. Herein, a cluster‐defect engineering (CDE) strategy is employed to modify the pristine UiO‐66 framework, wherein Zn incorporation followed by selective acid etching yields defect‐rich A/(Zn,Zr)UiO‐66 catalysts featuring hierarchical porous architectures and abundant Lewis (L) acid sites. Optical and photoelectrochemical analyses confirm that CDE broadens visible‐light harvesting, narrows the bandgap, and prolongs carrier lifetimes. The synergistic interplay between L acid sites and photocatalysis over A/(Zn,Zr)UiO‐66 results in an excellent photocatalytic performance in biodiesel production via oleic acid (OA) esterification with methanol (CH 3 OH) under mild reaction conditions, outperforming pristine UiO‐66. Notably, the optimized A/(Zn,Zr)UiO‐66‐0.2 achieves a remarkable 99.3% biodiesel yield under mild conditions, alongside superior stability and reusability. Further, in situ spectroscopic investigations and density functional theory (DFT) calculations disclose that CDE lowers the coupling barrier of OA and CH 3 O• radicals by strengthening OA adsorption and activation as well as facilitating charge stabilization at unsaturated Zr sites. This work highlights CDE as an ingenious strategy for tailoring the electronic configuration and interfacial chemistry of MOFs, offering a versatile platform for visible‐light‐driven biomass upgrading and sustainable fuel production.

FireSmoke-FL: a privacy-preserving federated learning framework for real-time fire and smoke detection

Crystal Engineering of Intrinsic Dynamicity in Metal‐Organic Frameworks for Adaptive Multicomponent Catalysis

ABSTRACT Metal‐organic frameworks (MOFs) provide unique catalytic environments through steric confinement imposed by their pores that govern reactivity, but concomitantly limit complex multicomponent transformations. Here, we first report a crystallography‐guided design of intrinsically dynamic MOFs that overcome this longstanding challenge. A crystallography–catalysis feedback loop with dimensionality and ligand‐flexibility tuning built a homologous Zn‐MOF series, revealing intrinsically dynamic, layer‐pillared Zn‐Bpe as the optimal catalyst. Mechanistic studies with a ligand‐substituted rigid analogue, host‐guest binding, density functional theory (DFT), and ab initio molecular dynamics (AIMD) reveal an adaptive catalytic mechanism where guests induce in situ framework dynamics, enhancing the diffusion of the substrates and the activity of the catalytic center. This dynamicity enables efficient and selective multicomponent couplings, exhibiting broad substrate tolerance and functional group compatibility, including a tandem domino Petasis reaction. Our findings establish intrinsic dynamicity as a generalizable design principle in MOF catalysis, balancing accessibility, selectivity, and structural integrity in complex transformations.

Edge-prior and reliability-guided collaborative learning for white blood cell classification

Cyclo‐Polyproline: Chameleonic All‐Peptide Macrocycles With Induced‐Fit Host‐Guest Recognition

ABSTRACT We report the design, synthesis, and characterization of a novel class of all‐peptide macrocycles, Cyclo‐Polyprolines ( CP ). Exploiting the precision of Fmoc‐based solid‐phase peptide synthesis (SPPS) and head‐to‐tail macrocyclization, this platform grants unparalleled control over the macrocycle's primary sequence and secondary structure, offering a viable route toward exo ‐/ endo ‐functionalization and addressing a bottleneck of traditional synthetic host macrocycles. The resulting CP scaffold is highly amphiphilic, exhibiting excellent solubility in both organic and aqueous media. Structural analysis via NMR spectroscopy and single‐crystal x‐ray diffraction reveals a distinct chameleonic character: the macrocycle shifts from an all‐junctions‐ cis conformation in organic solvents to a predominantly all‐junctions‐ trans isomer in water. We demonstrate that this transition is driven by a cooperative hydration effect, wherein water molecules stabilize the expanded framework through precise two‐point hydrogen bonding. Demonstrating responsive host‐guest capabilities, CP undergoes induced‐fit isomerization to bind ligands, successfully forming, among other species, an all‐peptide pseudo‐rotaxane. This methodology establishes a robust platform for creating functionalized, proline‐based hosts with significant potential in medicinal chemistry, drug delivery, and organocatalysis, thereby bridging the gap between supramolecular systems and enzyme mimetics.