Browse Articles

Adaptive Restructuring toward Intrinsically Stable Rh Catalyst during Water–Gas Shift Reaction

ABSTRACT Achieving intrinsic stability of reaction‐formed catalytic sites, and understanding its origin, remains a central challenge in heterogeneous catalysis. Although CO‐driven restructuring of atomically dispersed metals into subnanometer clusters has been observed in methane reforming and related reactions, the electronic basis of the resulting stability and the catalytic mechanism on these sites remain unknown. In this study, we show that atomically dispersed Rh on CeO 2 nanorods spontaneously evolves into Rh 3 (CO) 4 clusters during the water–gas shift (WGS) reaction, and that this restructuring resolves the inherent activity–stability trade‐off. Metastable Rh 3 (CO) 3 clusters with higher initial activity transform into thermodynamically stable Rh 3 (CO) 4 that sustains performance over 5000 h at 300°C without apparent deactivation. Combining in situ spectroscopy, kinetic analysis, and density functional theory calculations, we reveal the dual origins of this intrinsic stability. Coordination of the fourth CO ligand lowers the cluster formation energy by 2.15 eV, driven by ‐π* hybridization through Rh‐to‐CO back‐donation, rendering Rh 3 (CO) 4 a thermodynamic sink resilient to reaction‐induced perturbations. Meanwhile, surface hydride species generated at oxygen vacancies open a concerted COOH dehydrogenation pathway, markedly lowering the rate‐determining barrier. This work demonstrates that reactive atmospheres can steer catalytic sites toward configurations where structural stability and catalytic function coexist.

Effect of platelet-rich plasma on pain, function, and graft maturation after anterior cruciate ligament reconstruction: a prospective, randomized controlled trial

Technologies to measure and modulate protein subcellular localization

Generation of the Camptothecin Scaffold by a Flavin‐Catalyzed Photooxidative Skeletal Reorganization

ABSTRACT The plant alkaloid camptothecin is a high‐value precursor for the semi‐synthesis of multiple anticancer drugs. The key transformation during its biosynthetic pathway is a yet enigmatic skeletal reorganization from a 6/5/6 tetrahydro‐β‐carboline ring system to the 6/6/5 pyrroloquinoline scaffold, which is characteristic of camptothecin‐related alkaloids. Here, we show that this scaffold transition can be efficiently catalyzed by flavin cofactors such as flavin mononucleotide in a photooxidative process. As part of this complex transformation, we verified the existence of a previously postulated macrocyclic ketolactam intermediate. Based on the mild conditions—oxygen, light, and flavins—we show that this conversion can also take place in leaves of Nicotiana benthamiana , a plant which does not normally produce camptothecin or related alkaloids. Our optimized biomimetic photochemical reaction conditions enable a short, mild, and efficient semi‐synthesis of the alkaloids (3 S )‐pumiloside, (3 R )‐pumiloside, and vincosamide ketolactam, also known as turpiniside, without any protecting groups. Thus, our work improves our understanding of this key skeletal reorganization step forming the camptothecin scaffold in nature and provides streamlined photocatalytic access to camptothecin‐related alkaloids.

Self-adaptive cyber deception and resilient network defense via adversarial environment simulation

Abstract In the dynamic world of cybersecurity, the attacker is constantly innovating his methods of attack while taking advantage of vulnerable unknown to defender reactive defense is increasingly inadequate. This paper presents a novel approach for proactive cyber defense- autonomous system, which combines cyber deception, adversarial environment simulation, and self-adaptive reinforcement intelligence. At the core of this approach are dynamic and life-like attack vectors created through Generative Adversarial Networks (GANs) to mimic real-world zero-day and polymorphic threats. These artificially adversarial scenarios make the training environment very unstable for the DRL agent in the sense it has to learn robust context aware defense policies when the enemy is changing its attack strategies on the fly. Through a sequence of sustained exchange with GAN-generated environment, the DRL agent can be trained to identify malice with a non-trivial set of malware behaviors beyond finite rules or static signatures. Whereas traditional IDS/IPS solutions (i.e., performed respectively after-the-fact and by rule-based actions) simply aim to mitigate an attack, the latter moves the goalposts by transforming the surface of attack-defense continuously into a battlefield, and by employing, among others, deception nodes, re-routing detection vectors, and risk posture adaptation as the threat context changes. The observer is not only robust to novel attacks but also triggers deceptive traps on the attacker and confounds attackers’ inference paths, leading to increased robustness as well as lower false alarms and reduced compromise-recovery time. We run our method on a synthetic smart-grid network where we inject good and adversarial traffic into the network so that we can evaluate the resilience under multiple attack scenarios in a fine-grained manner. Empirical study in various network scenarios shows that the effectiveness of proactive threat detection, defense strategy optimization and recovery performance can be significantly improved MTTC by approximately 4.5× compared to static IDS, while reducing FPR by over 75%, demonstrating substantial gains in both detection reliability and response efficiency. The proposed model serves as a cornerstone toward the development an autonomous, digital immune system that learns, evolves, and turns even the most lethal forms of malware, ransomware, and zero-day attacks into benign files without human intervention—to move from static defense to dynamic, intelligent cyber-resilience.

Hydrophobic Promoter‐Enhanced Tandem Catalysis for Alkene Epoxidation With H ₂ and O ₂

ABSTRACT The efficiency of tandem catalysis is fundamentally limited by the transport of transient intermediates. In the direct epoxidation of alkenes with H 2 and O 2 , in situ generated H 2 O 2 rapidly decomposes during diffusion, rendering most Ti active sites kinetically inaccessible and imposing a long‐standing performance ceiling. Here, we overcome this limitation by engineering hydrophobic transport channels via physical integration of a hydrophobic polymer with bifunctional Au/TS‐1 catalysts. This microenvironment accelerates H 2 O 2 migration away from hydroxyl‐rich surfaces toward remote Ti sites while suppressing nonproductive decomposition. Molecular dynamics simulation studies show that the diffusion of H 2 O 2 on hydrophobic surfaces is significantly higher than on hydrophilic surfaces, as reflected experimentally by a 25% increase in tandem H 2 O 2 efficiency. Moreover, the hydrophobic channels promote rapid desorption of epoxide products, suppressing ring‐opening reactions and carbonaceous accumulation, resulting in a stable ∼90% epoxide selectivity over 200 h. This strategy exhibits broad generality across Au–Ti bifunctional catalysts for alkene epoxidation using in situ generated H 2 O 2 , with an outstanding H 2 utilization efficiency of 73.5% achieved over the Au/TS‐1‐B catalyst under the identical standard reaction conditions employed throughout this work. This work establishes diffusion control of metastable surface species as a principle for breaking intrinsic transport–decomposition trade‐offs in tandem catalysis.

BIBOP‐Catalyzed Asymmetric Staudinger/aza‐Wittig Reaction: Unified Syntheses of (–)‐Minfiensine and (+)‐Aspidophylline A

ABSTRACT A unified approach has been developed to construct the characteristic 4a,9a‐heterocycle‐fused tetrahydrocarbazole skeleton present in various monoterpene indole alkaloids. This method hinges on a unique chiral bisphosphine BIBOP‐catalyzed asymmetric Staudinger/aza‐Wittig reaction followed by imine cyclization. Compared to conventional mono‐ and bisphosphines, BIBOP exhibits more robust performance across diverse reaction settings. Mechanistic studies revealed that BIBOP(O), the mono‐oxidized derivative of BIBOP, could also promote the asymmetric transformation with excellent enantioselectivity. Leveraging the developed method, we have accomplished a concise total synthesis of (–)‐minfiensine and a formal synthesis of (+)‐aspidophylline A. This work not only establishes a versatile platform for the synthesis of diverse monoterpene indole alkaloids but also offers a new class of organophosphine catalysts applicable to asymmetric Staudinger/aza‐Wittig reaction as well as related transformations.

Simulation-based assessment of solar-integrated systems for climate-resilient residential buildings in semi-arid regions

Asymmetric Ionic Liquid Modulated Anion‐Reinforced Electric Double Layer for Advanced Durable Lithium Batteries

ABSTRACT The electric double layer (EDL) governs local electrolyte enrichment and reduction pathways, thereby directing the nucleation and evolution of solid electrolyte interphase (SEI). However, electrolyte design is still largely guided by bulk solvation descriptors. Here, an asymmetric room temperature phosphonium ionic liquid, (2‐methoxyethoxy)methyl phosphonium hexafluorophosphate (PMEP), is designed to promote an anion‐reinforced EDL. Molecular asymmetry lowers the melting point of PMEP and promotes PF 6 − participation in Li + ‐centered solvation structures. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations suggest that PF 6 − can participate in Li + ‐centered interfacial solvation clusters under selected charge states, which contributes to the formation of an SEI containing both organic reduction products and inorganic species such as LiF and Li 2 O. This organic/inorganic SEI structure lowers interfacial impedance and the apparent activation barrier for Li + transfer, enabling more uniform lithium deposition and a mechanically robust interface. Li|LiFePO 4 batteries with an areal loading of 11.3 mg cm −2 deliver 94.9% capacity retention after 600 cycles. The fabricated 1.6 Ah Graphite|LiFePO 4 cylindrical cell operates stably for over 500 cycles with a Coulombic efficiency above 99.8%. This work demonstrates a shift in electrolyte design from bulk formulations toward interfacial solvation structure engineering for next generation batteries.

Identification of DNA sequence variants in the Vasculo-Behcet disease patient using whole exome sequencing: a pilot study from Pakistan

AND‐Logic‐Gated Aptamer Switch for Precise Targeting and Regulation of RNA G‐Quadruplexes

ABSTRACT RNA G‐quadruplexes (rG4s) play critical roles in gene regulation and cancer progression, yet their precise manipulation in tumor cells remains challenging. rG4‐targeting L‐RNA aptamers are an emerging class of ligands with exceptional affinity for rG4s; however, their lack of cell type‐specific delivery hinders their regulatory and therapeutic potential. Herein, we engineer an activatable bispecific aptamer switch, termed the Allosteric RNA G‐quadruplex ON‐switch (ARGON), which integrates an rG4‐targeting L‐RNA Apt.4‐1c module (masked by a glutathione (GSH)‐cleavable lock strand) with a tumor receptor‐targeting Sgc8 DNA aptamer to precisely target rG4s and regulate downstream cellular activities within tumor cells. The AND logic‐gated ARGON is activated exclusively in tumor cells that exhibit both tumor receptor overexpression and elevated GSH levels. Following cellular uptake, GSH‐triggered lock cleavage exposes L‐Apt.4‐1c's rG4‐binding domain, enabling binding oncogenic Bcl2 rG4. Then activated ARGON regulates rG4‐associated tumor cellular functions while sparing normal cells. Besides, we apply ARGON to target human telomerase RNA component ( hTERC ) rG4 to show our method's generality. Collectively, by integrating cell‐surface addressing with intracellular environmental sensing, our work reports an “old‐chemistry‐new‐trick” framework for regulating nucleic acid structures, enabling conditional targeting of cellular RNA structures with minimal off‐target effects and propelling aptamer‐based precision biomedicine forward.

A multimodal learning framework for Arabic handwritten word recognition and future research directions

Achieving High Selectivity and Stability in Electrocatalytic CO ₂ Reduction in Acidic Media via Ion Confinement

ABSTRACT Immobilizing cation‐type organic molecules at the cathode represents a transformative strategy for enhancing the electrocatalytic CO 2 reduction reaction (CO 2 RR) in acidic or pure water. However, the investigation of anion‐type organic molecules is missing, and the roles of cations and anions are not well understood, especially in the membrane electrode assembly (MEA) configuration. Employing an ionic‐confinement strategy mediated by a solid‐state electrolyte, we systematically investigate the influence of cation‐ and anion‐type organic molecules on CO 2 RR. Our findings show that cations in both cation‐ and anion‐type molecules play a crucial role in inhibiting the hydrogen evolution reaction and promoting CO 2 RR in MEA. Utilizing an anion‐type organic molecule, we achieved exceptional CO Faradaic efficiencies of 98.4% in H 2 SO 4 media (pH = 1) and 95.8% in pure water‐fed MEAs on Ag. Additionally, with cation‐type organic molecules, we demonstrated robust operational stability of 150 h in H 2 SO 4 (pH = 1) electrolyte and 460 h in an ultra‐low potassium concentration (2 mM) acidic electrolyte in MEA configuration. This work establishes a versatile framework for achieving high‐efficiency, long‐term CO 2 electrolysis across diverse electrolyte environments, highlighting its potential for industrial‐scale application.

Tenapanor reduces phosphate binder pill burden among hemodialysis patients in a post hoc phase 3 analysis

Abstract Using phosphate binders (PBs) to control hyperphosphatemia in patients undergoing hemodialysis is associated with substantial pill burden. In this post hoc phase 3 analysis, we evaluated the benefit of the selective sodium/hydrogen exchanger isoform 3 inhibitor, tenapanor, in reducing pill burden in these patients. Patients received oral tenapanor starting at 5 mg twice daily and PBs. Dose adjustments of PBs and tenapanor were based on serum phosphorus levels. Changes in daily PB pill count, daily equivalent dose of PBs, number of combined PBs used, PB dose frequency, and tenapanor dose at Week 50 were analyzed according to patient background factors. The analysis comprised 204 patients (followed up for Week 50: 154 patients). Factors affecting the tenapanor dose at Week 50 were sex ( P  = 0.029), age (< 65 vs. ≥ 65 years; P  = 0.008), normalized protein catabolic rate (< 0.80 vs. ≥ 1.00; P  = 0.019), presence of diabetic nephropathy ( P  = 0.038), constipation ( P  = 0.015), and the occurrence of diarrhea as an adverse event ( P  = 0.009). Tenapanor consistently reduced the daily PB pill count and equivalent dose of PBs from baseline to Week 50 across all patient background factors evaluated (all P  < 0.001 vs. baseline), thus demonstrating the clinical benefit of tenapanor regardless of patient background characteristics. Clinical Trial Registration ClinicalTrials.Gov (NCT04771780)

Unsaturated Amide Chemistry Enables Ultralong‐Cycling Zn Anode

ABSTRACT Vigorous side reactions and uncontrolled Zn deposition compromise the interfacial stability of Zn anodes, severely impeding the implementation of rechargeable aqueous Zn metal batteries (RAZMBs). Developing facile and efficient strategies to mitigate these issues and achieve ultralong‐cycling Zn anodes remains challenging. Herein, an ultralong‐cycling Zn anode is realized via unsaturated amide chemistry. Specifically, amide‐based surfactants with polar groups (e.g., ─NH 2 ) and unsaturated bonds (e.g., C═C) served as electrolyte additives that specifically adsorb onto Zn anodes, reconstruct the inner Helmholtz plane (IHP) structure, and in situ form a dynamic polymer film (DPF) through electropolymerization during Zn deposition. The tailored IHP and in situ formed DPF synergistically enable a hybrid interphase integrating inorganic rigidity and organic flexibility, which not only effectively suppresses parasitic reactions, regulates Zn 2+ diffusion, and homogenizes Zn deposition, but also accommodates plating/stripping volume variations. Notably, with acrylamide (AAM) as a representative additive in ZnSO 4 ‐H 2 O electrolyte, the Zn||Zn symmetric cell delivers an ultralong cycle life of 5500 h (at 1.0 mA cm −2 and 1.0 mAh cm −2 ), outperforming most reports. These results suggest that the synergistically tailored IHP and in situ formed DPF driven by unsaturated amide chemistry can facilely and efficiently stabilize Zn anodes, providing a promising strategy for the practical application of RAZMBs.

A dual-layer hybrid path planning method for autonomous vehicles via multi-strategy enhanced GWO and adaptive DWA

Subcellular localization as a driver of protein function

Nitrogen‐Doped CeO _2‐x Supports Accelerate Interfacial Water Dissociation at Surface Pt Sites for Durable Industrial Alkaline Hydrogen Evolution

ABSTRACT Surmounting the high kinetic barrier of water dissociation is a prerequisite for efficient alkaline hydrogen evolution reaction (HER). Herein, we present a nitrogen‐doping strategy for CeO 2‐x supports to tailor the interfacial water microenvironment at supported Pt sites. By leveraging distinct ligand‐directed metal–organic framework precursors, we construct well‐defined Pt−N/O−Ce interfacial coordination motifs. Nitrogen doping not only stabilizes ultrafine Pt clusters via enhanced metal–support interactions but also triggers pronounced interfacial electronic redistribution. Crucially, operando surface‐enhanced Raman spectroscopy reveals that the Pt−N/O−Ce interface promotes the accumulation of weakly hydrogen‐bonded K + ·H 2 O species, which disrupts the rigid interfacial water network and accelerates the rate‐determining water dissociation step. Consequently, the obtained catalyst with Pt−N/O−Ce interface delivers a remarkable mass activity of 13.6 A mg −1 Pt at 100 mV overpotential for HER, representing a 7.6‐fold enhancement over its N‐free counterpart. Demonstrating industrial viability, the Pt/N‐CeO 2‐x @NC achieves 1 A cm −2 at 1.73 V in a large‐area (25 cm 2 ) anion‐exchange membrane water electrolyzer, maintaining exceptional durability over 1600 h at 80°C (degradation rate of 87.5 µV h −1 ). This work elucidates the critical role of N‐mediated interfacial engineering in breaking the water dissociation bottleneck for robust industrial‐scale alkaline electrolysis.

Machine learning-assisted identification and validation of NRP1 inhibitors through molecular docking and dynamics simulations

Photocatalyzed Hydro‐acrylonitrilation of Alkenes

ABSTRACT The catalytic cyanation of alkene feedstocks is a powerful method for introducing highly versatile alkenyl nitrile moieties into organic molecules. These reactions have traditionally relied on transition metal catalysts, hazardous nitrile sources, or prefunctionalized alkenes, which have restricted their potential application in drug discovery. Here, we present the first photocatalytic hydro‐acrylonitrilation of free alkenes using stable 4‐cyano‐3‐oxotetrahydrothiophene (c‐THT) as the cyano source to produce fused alkenyl nitriles with broad substrate scope and excellent functional group tolerance. Unlike previous polar catalysis, c‐THT was first applied in visible‐light catalysis as an acrylonitrile surrogate, allowing this radical‐mediated reaction to occur under operationally simple and mild conditions and enabling numerous functionalized activated and nonactivated alkenes to proceed acrylonitrilation in a highly efficient manner. The synthetic utility was further demonstrated by the gram‐scale preparation and downstream synthetic elaboration toward various valuable building blocks.