Browse Articles

Dual Active Sites in a Single MOF: Achieving High‐Rate and Selective Photocatalytic CO ₂ Reduction to Formate With Concurrent Water Oxidation

ABSTRACT A critical challenge in artificial photosynthesis is the limited availability of photocatalysts that effectively integrate active sites for both CO 2 reduction and water oxidation reactions. Herein, we first use defect engineering to integrate the ruthenium 2,2'‐bipyridine‐6,6'‐dicarboxylic acid Ru(bda) 3+ moiety, renowned for its photosensitivity and water‐oxidizing capabilities, into the CO 2 ‐reducing NH 2 ‐UiO‐66 framework, that is, d ‐MOF/Ru. The photoelectrochemical and in situ XPS measurements reveal that the Ru(bda) 3+ sites fulfill a dual function: enhance visible‐light absorption and promote charge separation, while simultaneously serving as active centers for water oxidation. Remarkably, enabled by the concurrent water oxidation activity at the Ru(bda) 3+ sites, the d ‐MOF/Ru generates HCOOH at a rate of 2157 µmol g cat. −1 h −1 with 99.7% selectivity under visible light irradiation, a performance 500 times greater than that of pristine NH 2 ‐UiO‐66. Furthermore, in situ DRIFTS and theoretical calculations indicate that Zr‐oxo clusters promote CO 2 reduction while Ru(bda) 3+ sites drive water oxidation in a synergistic cycle. This work presents a molecular‐level strategy for optimizing photocatalysts, offering new perspectives for improving the efficiency of artificial photosynthesis.

Integrated transcriptomic network analysis reveals shared immunogenomic regulators between glioma and type 2 diabetes, highlighting VCAN as a prominent marker

Photocaged Oxytocin and Vasopressin Probes to Decipher Neuropeptide Signalling With High Spatiotemporal Resolution

ABSTRACT The oxytocin/vasopressin (OT/VP) neuropeptide signalling system is essential for regulating social behaviour, emotion, learning, and memory, and its dysregulation is associated with multiple neurological disorders. However, accurately studying OT/VP signalling in the brain remains difficult due to widespread receptor expression, long peptide half‐lives, and extensive diffusion. To address these challenges, we investigated three classes of photolabile protecting groups—coumarin, nitrophenylpropyl, and borondipyrromethene—to enable precise, light‐triggered OT/VP release. These photocages allow controlled activation with one‐photon (365–527 nm) or two‐photon (730–780 nm) irradiation and do not generate cytotoxic by‐products. Using these cages, we synthesised OT/VP photoprobes and characterised their photopharmacological properties at their neuronal receptors (OTR, V 1a R, V 1b R). The coumarin cage proved the most effective, suppressing OT/VP bioactivity until rapid photouncaging enabled on‐demand receptor activation. It excelled in cellular assays, primary rat hippocampal neurones, and ex vivo acute mouse brain slices, demonstrating broad applicability. It is biocompatible, readily incorporated into peptides, and compatible with various neuronal experimental setups. Photo‐uncaging can be performed with inexpensive light‐emitting diode (LED) setups, as well as with extreme precision via two‐photon excitation, enabling investigations of neuropeptide signalling with high spatiotemporal resolution, offering new opportunities to investigate neuropeptide function in health and disease.

Effect of preparation method and edible oil type on the formation of PAHs in popcorns

A NIR‐Gated Nanogenerator Enables Low‐Dose Nitric Oxide‐Potentiated Phototherapy

ABSTRACT Light‐activatable nitric oxide (NO) donors are promising for precision cancer therapy but are hindered by premature leakage and a reliance on high dosages that may lead to off‐target cytotoxicity. Herein, we report a near‐infrared (NIR)‐gated nanogenerator (Cy‐NO NPs) engineered for low‐dose, NO‐potentiated multi‐modal cancer phototherapy. By anchoring a thiol‐functionalized ortho‐trifluoromethyl‐nitroaromatic moiety onto a cyanine (IR825) scaffold, the design ensures negligible NO leakage under oxidative, reductive, and thermal stresses, thereby eliminating systemic toxicity. Upon 808 nm excitation, the excited‐state energy dissipation is balanced to drive four concurrent pathways: (i) a photoinduced intramolecular electron transfer (PIET) process triggering a nitro‐to‐nitrite rearrangement for NO release; (ii) Type I & II photodynamic effects; (iii) photothermal conversion; and (iv) NIR‐II fluorescence emission. The released NO reacts in situ with simultaneous superoxide (O 2 •− ) bursts to yield highly cytotoxic peroxynitrites (ONOO − ). This synergistic ROS/RNS surge targets mitochondria, inducing membrane depolarization and rapid ATP depletion to trigger apoptosis. Guided by NIR‐II fluorescence imaging, this multi‐modal therapy achieves efficient tumor ablation in vivo, validating a potent low‐dose strategy for integrating controlled gas release with phototherapy.

Depressive symptoms mediate the longitudinal link between sleep duration and subjective well-being in middle-aged and older Chinese adults

UAV-based tree species classification using DenseNet121 with transfer learning on visible light images

Anion Size‐Dependent Conformational Folding of Guanidinopropionate: Enabling Tunable Birefringence and Balanced Second‐Harmonic Generation Performance

ABSTRACT The structure–property relationship investigations constitute a fundamental paradigm for the rational design and synthesis of high‐performance functional materials. Herein, four guanidinopropionates (C 4 H 10 N 3 O 2 )X (X = Cl– (GPC), Br − (GPB), [HSeO 3 ] − (GPSe), and [NH 2 SO 3 ] − (GPMS)) were reported. Anion‐size‐dependent modulation of the C2─C3 single bond rotation (linking guanidino and carboxylic π‐conjugated groups) induces a reduction of the dihedral angle between the two π‐conjugated planes ( α ) from 175° to 65°. With such a coplanarity reduction, the optical anisotropy property (birefringence, Δ n ) decreases from an excessive 0.20 in GPC to a favorable 0.11 in GPMS. Remarkably, GPMS also exhibits a large band gap (5.63 eV) and an enhanced second‐harmonic generation (SHG) response (3.3 × KH 2 PO 4 ). DFT reveals these four conformations are nearly degenerated, and the HOMO–LUMO gap, polarizability anisotropy, and hyperpolarizability across these four conformers are broadly tunable. This work first demonstrates how conformational folding control of flexible π‐conjugated units effectively modulates and optimally balances three critical yet mutually restrictive parameters essential for high‐performance SHG materials.

A dynamic nomogram for predicting the need for invasive interventions in patients with tubo-ovarian abscess

Photolyzable Polymer Brushes: Subtractive 3D Structuring of Surfaces Using Water and Light

ABSTRACT Polymer brushes are a key technology for designing surfaces, with applications in biomedicine alone including biosensing, cell culture, regenerative medicine, and antibacterial coatings. The structuring of polymer brushes has the potential to precisely tailor interfaces for specific application requirements. However, complex fabrication processes can limit the applications of polymer brushes. Herein, a subtractive patterning process is reported, which decouples initial fabrication from the structuring process. Using radical ring‐opening polymerization of cyclic monomers with photocleavable cyclobutane rings, photodegradable targets are directly embedded into the polymer brush main chains. After the initial fabrication, these brushes can be readily degraded with light, triggering photocleavage of the cyclobutane units. This enables continuous brush degradation of over 50% of brush height for topographical patterning without affecting brush properties such as hydrophilicity and adhesion force. The inherent photodegradability of the polymer brush eliminates the need for additional chemicals or catalysts and can be carried out using nothing but water and light at ambient temperature.

Phytochemical signatures and multifunctional bioactivities of two Ocimum basilicum varieties (Obb vs. Obg): antimicrobial, antioxidant, and anticancer potential

Unraveling the Stability of N‐Doped Graphene Supported Single‐Atom and Dual‐Atom Catalysts From Pourbaix Diagram

ABSTRACT Single‐atom catalysts (SACs) and dual‐atom catalysts (DACs) exhibit great potential in heterogeneous catalysis. However, studying their stability under practical reaction conditions remains a challenge. This work theoretically studies the electrochemical stability of N‐doped graphene‐supported SAC and DAC of five metals (Cr, Mn, Fe, Co, and Ni) under different pH and electric potentials. We propose a universal method that not only considers the chemical speciation of leached metal in solution (ions, hydroxides, and oxyanions) but also introduces structural modification for the substrate vacancy (binding with H). By constructing pH‐potential dependent Gibbs free‐energy criteria, Pourbaix diagrams (stability) for each catalyst without and with adsorbates were plotted. The results show that Co‐ and Ni‐SAC possess good stability over a wide range of potentials and pH, and Co‐SAC can be further stabilized by adsorbates (*H, *OH, or *OOH). Fe‐SAC can only be stable with *H, *O, and *OOH, while Mn‐SAC only exhibits stability with *O, under certain potentials and pH. Cr‐SAC and Cr‐, Mn‐, Fe‐DAC are unstable under all conditions. The stable regions of DAC are generally smaller than those of SAC, indicating potential difficulties in synthesis and applications. This study provides a theoretical model for evaluating and screening durable catalysts in realistic applications.

The effect of struvite and triple superphosphate on lead immobilization in contaminated soil in the presence of malic acid

Single‐Atom Barium‐Mediated Hydrogen‐Bonding Interaction via Mortise‐and‐Tenon Interlock for Rechargeable Biomass Electrooxidation in Pure Water

ABSTRACT Electrooxidative upgradation of biomass‐derived molecules like 5‐hydroxymethylfurfural (HMF) offers a carbon‐neutral blueprint to produce valuable chemicals, with conversion efficiency highly relying on the strong base and costly membrane use. Herein, we anchor single‐atom Ba into nickel‐oxyhydroxide as the mortise of sulfate (tenon) to construct a rechargeable anode S‐Ba 1 Ni 1‐ x OOH for decoupling HMF electrooxidation, enabling quantitative 2,5‐furandicarboxylic acid (FDCA) production without alkali, potential, and membrane. This decoupling system involves i) active Ni 3+ −O (re)generation via charging and ii) extraction of H atoms of HMF with Ni 3+ −O to undergo deprotonation into FDCA (∼100% conversion and selectivity) in pure water without electricity (discharging). Hydrogen‐bonding interaction between surficial sulfate and hydroxide of HMF can accelerate the substrate migration toward solid–liquid interface with enhanced conversion. Theoretical calculations expound that hydrogen‐bonding interaction decreases the hybridization degree between O‐2p and H‐1s orbitals in O─H bond of HMF to heighten its H removability, thereby fostering complete HMF oxidation into FDCA. Various biomass derivatives are also amenable to this decoupling system, affording >96.3% yields for acids. Techno‐economic analysis illustrates that replacing strong alkali with pure water can reduce the production cost of FDCA by 50.5%, underlining the wide prospect of this decoupling strategy and endowing an attractive route for biomass valorization.

Design and implementation of a novel multilevel inverter for renewable energy applications

Solvent‐Regulated Lattice Elasticity and Pressure‐Induced Multi‐Stimuli Spin‐State Bistability in a Porous Hexagonal Framework

ABSTRACT Spin‐state switching in molecular materials becomes most effective when multiple external stimuli converge on a common structural pathway. Here we report a porous cyanide‐bridged {4d–3d} heterobimetallic framework formulated as {[Mo(CN) 8 ][Fe(v‐im) 4 ] 2 (BF 4 ).2DMF.H 2 O} n ( 1 ·2DMF·H 2 O ) (v‐im = 1‐vinylimidazole). Single‐crystal x‐ray diffraction reveals a flexible 3D hexagonal network where [Mo(CN) 8 ] 3 − units mediate magnetic communication through [Fe(v‐im) 4 ] nodes. Partial desolvation generates an elastic lattice ( 1 ·2DMF) that exhibits reversible thermally induced spin‐state switching with T 1/2  = 127 K and a pronounced light‐induced excited spin‐state trapping (LIESST) effect at T LIESST  = 60 K. In contrast, the fully solvated framework ( 1 ·2DMF·H 2 O) remains HS at ambient conditions, but switches under hydrostatic pressure, demonstrating structural matrix‐, stress‐ and squeeze‐driven bistability. The cooperative response originates from dynamic coupling between solvent molecules, counter‐ions, and the flexible framework, which collectively tune the spin‐state energetics. This study establishes elastic‐matrix squeezing as a unifying strategy for multi‐stimuli bistability and highlights the convergence of porosity, elasticity, and spin‐crossover behavior in adaptive molecular frameworks.

Determination of complex permittivity of a thin low-loss dielectric sample using state-space approach from waveguide measurements

Abstract An extraction procedure is proposed for relative complex permittivity ( $$\varepsilon _{rs}$$ ) determination of thin low-loss samples positioned/deposited on a supporting substrate material using waveguide non-resonant microwave measurements. Its substrate thickness and sample thickness independence makes it unique extraction method in comparison with the available retrieval methods which are free from either substrate thickness information only or sample thickness information only. Its theoretical model is constructed on the state-transition matrix and state vector through which the link between $$\varepsilon _{rs}$$ and measured scattering (S-) parameters is established. Compared with previous works in the literature, a closed form (explicit) expression of $$\varepsilon _{rs}$$ is derived for a two-layer (sample on a substrate material) composite structure, thereby eliminating any numerical analysis or tool. Numerical analyses are implemented for validation of the proposed method as well as assessing the effect of noise and any possible air gap between the sample and its substrate. X-band ( $$8.2-12.4$$ GHz) waveguide measurements of a thinner (around 1.00 mm) polyvinyl chloride (PVC) for different measurement scenarios and measurements of a thin zinc oxide film ( $$\cong 1.0 \mu$$ m) were performed to evaluate the performance of the proposed extraction method against other similar methods in the literature. Our method can find applications for $$\varepsilon _{rs}$$ characterization of thin-film, radar-absorbent material coatings, anti-corrosive paints, or thermal barrier coatings where sample thickness (and substrate thickness) can vary from one sample to another from the same batch.

Selective Electrocatalytic Hydrogenation of Phenol to Cyclohexanone at Industrial‐Relevant Current Density

ABSTRACT Electrocatalytic hydrogenation of biomass‐derived phenol represents a sustainable alternative route to produce value‐added chemicals such as cyclohexanone by replacing current energy‐intensive thermo‐catalytic processes. However, to date, the current densities of selective electrocatalytic phenol‐to‐cyclohexanone conversions are significantly lower than the requirements for industrial applications. Herein, we report a platinum‐palladium (PtPd) alloy electrocatalyst, exhibiting cyclohexanone production with 51% Faradaic efficiency and 88% selectivity at an industrial‐relevant current density of 565 mA cm −2 under −0.40 V versus reversible hydrogen electrode. Mechanistic studies indicate that the Pt sites catalyze active hydrogen species generation, which experience spillover to Pd, while Pd sites are responsible for phenol adsorption and hydrogenation, cooperatively promoting cyclohexanone production via a non‐competitive Langmuir–Hinshelwood mechanism. This work provides guidelines for the rational design of efficient electrocatalytic hydrogenation catalysts toward biomass upgrading at industrially relevant current densities.

Stabilizing fractional dynamical networks suppresses epileptic seizures

Precise Spatiotemporal Control of Sensory Nerve Blockade via Light‐Triggered Click‐Release Uncaging of 2′,6′‐Pipecoloxylidide

ABSTRACT The pursuit of non‐opioid analgesics remains a critical priority in pain management. Local anesthetics (LAs) are promising alternatives to opioids, yet conventional agents indiscriminately block both sensory and motor fibers, leading to motor impairment. 2′,6′‐Pipecoloxylidide (PPX) has emerged as a sensory‐selective LA, but its concentration‐dependent activity requires precise local control that current delivery systems cannot achieve. Here, we report a red light (660 nm)‐controlled liposomal platform that enables spatiotemporally precise release of PPX through a bioorthogonal photooxidation–click–release cascade. The system co‐encapsulates a photosensitizer (chlorin e6), dihydrotetrazine (6‐Pm‐DHTz), and trans‐cyclooctene‐modified PPX (TCO‐PPX). Upon 660 nm irradiation, 6‐Pm‐DHTz is oxidized to tetrazine, which rapidly reacts with TCO‐PPX to liberate active PPX within minutes. In vitro studies confirmed rapid, controllable release, while in vivo experiments in a rat sciatic nerve model demonstrated reproducible, light‐triggered sensory‐selective nerve blockade without motor dysfunction. The duration and intensity of anesthesia were tunable by adjusting irradiation parameters, and delayed activation remained effective up to 8 h post‐injection. The formulation exhibited excellent biocompatibility and prolonged local retention. This work establishes the first controllable platform capable of achieving purely sensory‐selective local anesthesia, representing a conceptual and technological breakthrough toward programmable, personalized, and non‐opioid pain therapy.