Browse Articles

Unveiling Volcano‐Type Trends in SOCT‐ISC Photosensitization: Energy Gap Law‐Guided Strategy for Efficient Photodynamic Therapy

ABSTRACT The development of high‐performance heavy‐atom‐free photosensitizers requires deep insight into their excited‐state dynamics. We report a series of cyanine‐based compounds functionalized at the C2 position that operate through spin–orbit charge transfer intersystem crossing (SOCT‐ISC). A pronounced “volcano‐type” relationship between photo‐induced electron transfer (PeT) efficiency and singlet oxygen quantum yield was uncovered. Femtosecond transient spectroscopy and quantum chemical calculations reveal that this trend stems from a dynamic competition between S 1 and T 2 intersystem crossing from the charge‐separated (CS) state and CS‐state charge recombination via internal conversion. The CS‐state energy serves as a key descriptor dictating this balance. By modulating the donor strength of the substituents, we optimized the CS‐state energy and identified TCy‐Pyr , a molecule near the volcano apex. TCy‐Pyr exhibits outstanding photodynamic performance, with in vitro and in vivo anticancer efficacy surpassing conventional benchmarks. It also displays aggregation‐induced targeting behavior, promoting selective tumor accumulation. This work elucidates the excited‐state dynamics in SOCT‐ISC systems and establishes a rational design strategy to overcome performance bottlenecks in photosensitizer development.

A robust stacked ensemble strategy with multi-optimizer CNN models for skin cancer classification

Enantioselective Total Synthesis of Breviones Utilizing a Bio‐Inspired Skeletal Editing Strategy

ABSTRACT Inspired by skeletal editing transformations in the biosynthesis of spiro diterpene pyrones, we herein present an enantioselective total synthesis of the meroditerpenoids breviones B, C, and N. Our synthetic strategy features a series of bio‐inspired skeletal editing transformations, including a Dowd–Beckwith ring expansion to construct the seven‐membered A‐ring, and an annulative skeletal rearrangement that couples terpene and α‐pyrone motifs into the spiro diterpene pyrone framework. This latter transformation involves a novel dihydropyran‐to‐dihydrofuran ring contraction, a strategy that has proven applicable to a diverse range of terpene and pyrone fragments. In addition, during the synthesis, we also developed a SnCl 4 ‐mediated intramolecular hydroalkylation of alkenyl β‐keto esters, which enables the concurrent assembly of the fused B/C ring system along with three contiguous stereocenters.

Factors affecting Iranian farmers’ intention to adopt digital agriculture: an integrated TPB-TAM approach

Charge‐Tunable Dense Dual‐Atom Nanozymes Reprogram Biothiol Metabolism Through Multi‐Enzyme‐Mimetic Catalysis to Synergistically Induce Ferroptosis and Disulfidptosis

ABSTRACT Biothiols play a pivotal role in maintaining cellular redox homeostasis, coordinating programmed cell death pathways, and modulating immune responses. Reprogramming biothiol metabolism in tumor cells thus presents a promising strategy for enhancing anti‐tumor immunity. Here, we report the rational design of a densely accessible heteronuclear Fe/Co dual‐atom nanozyme (FeCo DDA), which mimics natural flavoenzymes by coordinating high‐density Fe and Co active centers to regulate biothiol metabolism and induce intracellular disulfide accumulation. The dense heteronuclear diatomic catalytic center (with Fe and Co mass fractions of 10.35% and 11.32%, respectively) optimizes the Bader charge and d‐band center by adjusting electron redistribution, endowing it with excellent mimetic enzymatic activities for catalyzing the oxidation of biothiols to disrupt the homeostasis of tumor cells. Simultaneously, co‐loaded phlorizin inhibits glucose uptake, further driving compensatory cystine accumulation and disrupting glutathione biosynthesis. This dual action synergistically induces ferroptosis‐enhanced disulfidptosis, disrupting redox homeostasis and triggering immunogenic cell death. As a result, FeCo DDA co‐loaded with phlorizin (FeCo DDA/P) not only enhances tumor cell immunogenicity but also reshapes the immunosuppressive tumor microenvironment, thereby potentiating anti‐tumor immune responses. This work highlights a dual‐atom nanozyme strategy to reprogram tumor metabolism and orchestrate multimodal cell death for effective tumor immunotherapy.

Simulation and performance analysis of nanostructure-based perovskite solar cells for improving their efficiency

Stimuli‐Responsive Silsesquioxane Nanozymes for Organocatalysis in Water and Prodrug Activation in Cells

ABSTRACT Synthetic nanozymes have emerged as promising alternatives to natural enzymes for catalytic and therapeutic applications, yet their limited stability, aqueous compatibility, and catalytic scope impede broader utilization. Here, we report a mild, one‐step sol–gel synthesis that yields ultrasmall, water‐stable octa‐amino silsesquioxanes functioning as metal‐free nanozymes. These minimalistic nanostructures exhibit aldolase‐like organocatalytic activity in water and enable dynamic, stimuli‐responsive modulation of catalysis through reversible supramolecular aggregation and disaggregation triggered by specific chemical inputs, thus forming a multifunctional platform for tunable catalysis and biomedical applications. Structural simplicity, stability, and functional versatility together permit tunable, enzyme‐like catalysis in water without auxiliary surfactants or phase‐transfer additives. Furthermore, the nanozymes display high biocompatibility and efficient cellular internalization, enabling their use in living cells, for instance, as intracellular prodrug activators via retro‐aldol activation of a doxorubicin prodrug in human glioblastoma and metastatic melanoma cells, resulting in selective cytotoxicity. This system provides a cost‐effective, sustainable, and scalable platform for water‐compatible, metal‐free organocatalysis that bridges abiotic catalysis and biological function. These findings demonstrate how rationally designed silsesquioxane frameworks can emulate natural enzyme reactivity while integrating adaptive, stimuli‐responsive behavior, broadening the applicability of synthetic nanozymes to catalytic and therapeutic contexts.

Comprehensive evaluation of gas-bearing properties in ultra-deep basement reservoirs based on an optimizable support vector machine

4‐Dimethylaminophenol: A ‘Smaller’‐Molecule PPI Inhibitor Targeting the PSD95 GK Domain Against Ischemic Stroke

ABSTRACT Protein–protein interactions (PPIs) represent challenging yet promising therapeutic targets. This study identifies 4‐dimethylaminophenol, an ultralow molecular weight compound (137 Da) from a fragment‐based library, as a novel PPI inhibitor targeting the Guanylate Kinase‐like (GK) domain of postsynaptic density protein 95 (PSD95). The direct binding of 4‐dimethylaminophenol with PSD95 GK was confirmed by X‐ray crystallography. Crucially, we uncovered a previously unknown PDZ‐independent interaction between the PSD95 GK domain and neuronal nitric oxide synthase (nNOS). 4‐Dimethylaminophenol inhibited this PSD95/nNOS interaction, reducing nitric oxide (NO) overproduction and neuronal excitotoxicity, thus exerted neuroprotective effects in vitro and in vivo. Moreover, structure–activity relationship (SAR) study showed that the phenolic hydroxyl and dimethylamino groups were crucial to the activity, and the introduction of ortho‐halogen substitution could enhance binding affinity. Leveraging its established clinical application as a cyanide antidote, low molecular weight, blood–brain barrier permeability (BBB) and proven neuroprotection, 4‐dimethylaminophenol presents a promising neuroprotective lead for drug discovery targeting ischemic stroke. The study also highlights the potential of the smaller molecules as PPI inhibitors, offering new insights into drug development of small‐molecule PPIs.

Thermodynamic-microphysical coupling mechanisms of hydrometeor phase transitions during persistent wind turbine icing

Electrostatic Potential Tuning‐Driven Molecular Rotor Rotation in Isostructural Metal‐Organic Frameworks for C ₃ H ₆ /C ₃ H ₈ Separation

ABSTRACT C 3 hydrocarbon separation is a core process for refining high‐value‐added petrochemical products. However, due to the remarkably similar physicochemical properties of these molecules, metal‐organic frameworks (MOFs) typically encounter an inherent adsorption capacity‐selectivity trade‐off. The dynamic pore characteristics of molecular rotor‐functionalized MOFs offer a novel approach to address this challenge. Herein, we propose an electrostatic potential matching strategy to drive the rotation of molecular rotors within MOF, boosting C 3 H 6 /C 3 H 8 separation. By modulating the amino density in MOFs through crystal engineering, three isomorphous MOFs (CoNi‐PYZ, CoNi‐PYZ‐NH 2 , and CoNi‐PYZ‐2NH 2 ). CoNi‐PYZ‐2NH 2 with a highly electronegative pore surface precisely matches the C 3 H 6 molecules, driving the molecular rotor rotation within the MOF, endowing the framework with unique flexibility, and thereby exhibiting a distinctive gate‐opening effect toward C 3 H 6 . This grants CoNi‐PYZ‐2NH 2 exceptional C 3 H 6 /C 3 H 8 (50/50, v/v) selectivity (96.5), which is 13.8 and 21.4 times higher than those of CoNi‐PYZ and CoNi‐PYZ‐NH 2 and significantly enhances C 3 H 6 uptake at low pressure (30.6 cm 3 g −1 at 0.01 bar and 298 K). Moreover, it exhibits an excellent C 3 H 6 storage density of 0.785 kg L −1 . Dynamic breakthrough experiments validate its superior dynamic separation performance. This study establishes an electrostatic potential‐driven molecular rotor rotation strategy, providing valuable insights for the development of high‐performance adsorbents.

Revalorization of Arracacia xanthorrhiza waste for controlled carboxin release in potato crop

Selective Oxidation of Tertiary Silanes Enabled by Tandem Single Atom Cerium Catalyzed Water Splitting/Non‐Bonding Phosphorus Site Promoted Nucleophilic Substitution

ABSTRACT The utilization of heterogeneous catalysts, particularly single‐atom catalysts (SACs), to mimic or even supplant their homogeneous counterparts for building complex molecular architectures is a long‐standing objective in sustainable chemistry, however it remains a formidable challenge to date. Herein, we report a selective oxidation of tertiary silanes through a tandem process combining single‐atom cerium‐catalyzed water splitting with nucleophilic substitution promoted by a non‐bonding phosphorus site. This approach yields either silanols or siloxanes with exclusive selectivity and promising reusability. In the Ce‐SA/CN catalyst, the redox shuttle of the atomically dispersed cerium center activates water to hydroxylate SiH bond while suppressing silanol condensation. In contrast, the introduction of phosphorus sites in Ce‐SA/CNP creates an adjacent Lewis basic site that recruits and activates the –OH group of nascent silanols, thereby driving efficient interfacial dehydration to form disiloxanes. This work underscores microenvironment engineering of SACs as a pivotal strategy for steering complex reaction pathways and establishes a versatile platform for precise synthesis.

Hybrid market design for decentralized energy trading: multi-k double auction with enhanced stable matching

Abstract The rise of distributed energy resources (DERs) and sophisticated digital communication systems has led to the emergence of Peer-to-Peer (P2P) energy trading as a viable method for facilitating flexible, autonomous, and efficient energy exchange within Local Energy Communities (LECs). This paper proposes a novel market model for P2P energy trading by integrating a multi-k double auction framework with the Gale-Shapley stable matching algorithm and metaheuristic optimization. The multi-k double auction offers greater pricing flexibility compared to traditional mechanisms such as uniform, discriminatory, and pay-as-bid auctions. The trading price is computed using a weighted parameter k balancing buyer and seller preferences, where k is evaluated for static values (0, 0.5, 1) and optimized dynamically using Ant Colony Optimization (ACO). Buyer-seller matching is performed using a constraint-aware Gale-Shapley algorithm that respects buyers’ budget limits and sellers’ capacity constraints. The model is validated using realistic data derived from photovoltaic generation, load forecasts, and prosumer preferences based on the IEEE 13 and IEEE 37-node residential feeders. Simulations were conducted over hourly trading periods divided into bidding and power exchange intervals. In the present work, the proposed hybrid architecture achieves improved social welfare, fairness in price allocation, higher market liquidity, and enhanced satisfaction for participants. This framework establishes a scalable and adaptive decision-making process that supports stable, efficient, and equitable operations in decentralized energy markets.

RaPID Selection of Backbone Macrocyclic Peptides Targeting Akt2

ABSTRACT Backbone‐cyclic peptides (BMPs) are an attractive class of molecules appeared in diverse natural bioactive products. However, mRNA display technology coupled with ribosomal synthesis is intrinsically inapplicable to such peptide phenotypes due to loss of the C‐terminal peptide region linking to the mRNA genotypes. To overcome this issue, we have devised a new strategy to link the sidechain‐to‐S‐mainchain bond via an S ‐to‐ N acyl‐shift to connect BMPs to the C‐terminal fragment of the peptide. Here, we report the application of this strategy to construct a library of BMPs fused to cognate mRNAs. The library was applied for the selection of BMP ligands targeting Akt2, which is involved in the signal pathway to cancer pathogenesis. Consequently, BMP ligands against Akt2 were successfully uncovered from the library. The most potent Akt2 inhibitor, BMPakti‐3, showed 1.3 nM of dissociation constant and 34 nM of half‐maximal inhibitory concentration (IC 50 ). This system offers a unique platform for the de novo discovery of bioactive BMP ligands against various protein targets of interest.

Spatiotemporal patterns and underlying drivers of provincial agricultural green total factor productivity in China

Deep learning-based identification of N6-methyladenine sites via hybrid feature fusion and SHAP-driven feature selection

Amorphous/Crystalline Heterojunction Ni(OH) ₂ /Cu ₂ O(111) for Photoelectrocatalysis NO ₃ ⁻ ‐to‐NH ₃ : Positive Onset Potential, High Selectivity, and Complete Conversion

ABSTRACT Photoelectrocatalytic selective nitrate (NO 3 − ) reduction to ammonia (NH 3 ) offers a sustainable route for the green nitrogen cycle, overcoming the inherent limitations of standalone electrocatalysis and photocatalysis. The central challenge is developing an efficient photoelectrocatalyst that simultaneously reduces overpotential and maximizes NH 3 selectivity. Herein, an amorphous/crystalline heterojunction Ni(OH) 2 /Cu 2 O bonded by Cu‐O v ‐Ni, is constructed via photoelectrocatalytic interface regulation for synergistic photoelectrocatalysis (SPEC) NH 3 synthesis. Results demonstrate ∼100% light absorption efficiency and ∼90% high charge separation efficiency, enabling almost completely rapid 98.80% NO 3 − conversion with stable NH 3 FE (> 99%) and high selectivity (> 97%). A superior NH 3 yield of 1316.1 µmol h −1 cm −2 is attained, alongside an excellent positive onset potential of 0.322 V versus RHE. In situ experiments further reveal that crystalline Cu 2 O activates carriers to accelerate the rate‐determining step (N +5 → N +3 ), while amorphous Ni(OH) 2 significantly enhances electron extraction and *H accumulation for protonation (N +3 → N −3 ). Increasing potential shifts the system from electro‐assisted photocatalysis (activating Cu‐O···*NO 3 − sites) to photo‐assisted electrocatalysis (Cu 2 O → Ni(OH) 2 electron transfer), then to SPEC (efficient *H coupling) process. Further application to actual fertilizer plant wastewater achieves ∼90% NO 3 − removal efficiency and > 85% NH 3 selectivity, demonstrating promising scalability for efficient photoelectrocatalysis NO 3 − ‐to‐NH 3 with great environmental remediation potential.

Cardiac activity monitoring for the heart rate classification with enhanced BiLSTM model

A framework for Hough-based lane line detection with analytical assessment aided by CORDIC