Browse Articles

Reversed Quantum‐Well Engineering Unlocks Large Ultraviolet Chiral Nonlinear Optical Response in a Water‐Resistant 2D Hybrid Fluorozirconate

ABSTRACT Two‐dimensional (2D) chiral organic–inorganic hybrid metal halides (OIHMHs) are promising for chiroptical applications. However, conventional Ge/Sn/Pb‐based systems remain limited by narrow bandgaps and poor moisture stability. In this work, we report the first 2D chiral hybrid fluorozirconate, ( R/S ‐MBA)ZrF 5 (MBA = methylbenzylammonium), addressing these limitations through reversed quantum‐well engineering enabled by a high‐valent Zr─F framework. It features a unique reversed Type‐I quantum‐well electronic structure, where the [ZrF 5 ] inorganic layer acts as a dielectric barrier and the band‐edge states are localized on the organic MBA cations. This structure yields a wide bandgap of 4.60 eV, a short UV cutoff edge of 265 nm, and a high laser‐induced damage threshold exceeding 1251.58 GW/cm 2 , providing a broad transparency window toward the UV region. Furthermore, ( R/S ‐MBA)ZrF 5 exhibits a large SHG circular dichroism (SHG‐CD) response with an anisotropy factor of 1.05. More importantly, it overcomes the typical moisture‐sensitivity of OIHMHs, maintaining its structural stability and SHG‐CD response after a 7‐day water immersion. Structural analysis and theoretical calculations reveal this unusual water resistance is mainly attributed to the robust Zr─F framework and an effective cavity volume of 3.6%. This work highlights reversed quantum‐well engineering as a novel way to synthesize water‐stable and wide bandgap chiral nonlinear optical materials.

Techno-economic optimization of a hybrid microgrid with integrated backup storage and vehicle-to-grid functionality

Abstract This study presents the techno-economic optimization of a hybrid backup system integrated within an off-grid microgrid framework with electric vehicle (EV) grid-interaction capability. A real-world case study from a remote region in Egypt is used to evaluate system performance under realistic operating conditions. The optimization problem is formulated to minimize the net present cost (NPC) while ensuring system reliability using a penalty-based loss of power supply probability (LPSP). The system integrates photovoltaic (PV), wind turbines (WT), battery energy storage systems (BESS), hydrogen energy storage systems (HESS), and EVs. The novelty of this work lies in the development of a coordinated multi-storage energy management strategy that integrates BESS, HESS, and constrained EV participation within a unified optimization framework. The results show that the BESS-only configuration achieves the lowest cost (NPC ≈ $20.33 billion), while the PV/WT/BESS/HESS configuration results in the highest cost (NPC ≈ $25.48 billion). The proposed PV/WT/BESS/HESS/EV configuration provides a balanced solution with an NPC of approximately $22.79 billion while maintaining near-zero LPSP. EV integration enhances system flexibility, reducing the required BESS capacity by 44.8% relative to the HESS-only configuration, while also lowering reliance on hydrogen-based long-term storage, thereby mitigating the high capital costs associated with extended-duration storage components. These findings demonstrate that coordinated multi-storage management significantly improves the techno-economic viability and operational resilience of large-scale off-grid microgrids in remote regions.

Mitigating Stress‐Induced Nonphotoactive Phase Transition Through Sodium Sulfonate Engineering for Stable and Efficient Perovskite Solar Cells

ABSTRACT Formamidinium lead triiodide (FAPbI 3 ) perovskite solar cells (PSCs) have attracted significant attention due to their outstanding optoelectronic properties. However, their long‐term stability remains limited by lattice strain‐induced transition from the photoactive α‐phase to the nonphotoactive δ‐phase. In this work, first‐principles calculations reveal that the incorporation of Na + into interstitial sites between adjacent FA + cations significantly reduces the formation energy of the α‐phase, thereby promoting its thermodynamic stabilization. Then, experimental results confirm that the introduction of 2 mol% Na + effectively alleviates lattice strain while simultaneously suppressing δ phase. Moreover, the accompanying sulfonate groups interacting with PbI 2 can regulate the crystallization and improve film quality. As a result, the optimized PSC achieved power conversion efficiency (PCE) as high as 26.67% (certificated 26.44%), ranking among the highest reported for the n‐i‐p structured devices. Notably, the bare device without encapsulation retained over 90% of its initial efficiency after continuous heating at 85°C for 1200 h and maintained 80% after 800 h continuous illumination. This study demonstrates that metal cation doping is an effective strategy for stabilizing the perovskite lattice and enhancing long‐term operational stability of perovskite‐based optoelectronic devices.

A three-way decision-making method integrating prospect theory and intuitionistic fuzzy similarity for air quality index big data

Tunable Oxygen Connectivity in Carbaporphyrinoid Polymers on Metal Surfaces

ABSTRACT Controlling oxygen‐mediated connectivity at metal surfaces offers a powerful route to engineer covalent and metal–organic architectures with atomic precision. Here, we demonstrate tunable oxygen‐based connectivity in carbaporphyrinoid polymers on Au(111) under ultrahigh vacuum (UHV) conditions. Initial thermal activation of hydroxyl‐functionalized dicarbahemiporphyrazine precursors induces carbon–carbon coupling via a [3+3] cycloaromatization, affording one‐dimensional polymers equipped with hydroxyl‐terminated units. From this intermediate two distinct oxygen‐based linkages can be achieved: further annealing induces dehydrogenative coupling of adjacent polymers through the hydroxyls groups to yield dibenzo‐p‐dioxane (O‐heterocyclic) bridges that covalently connect the carbaporphyrinoid macrocycles, whereas dosing cobalt produces extended metal–organic networks stabilized by two‐fold O···Co···O coordination motifs accompanied by cobalt‐metalated macrocycles. Scanning tunneling microscopy (STM) and non‐contact atomic force microscopy (nc‐AFM) directly resolve both the coordinated networks and the O‐heterocyclic bridging motifs. Complementary DFT and Free energy calculations elucidate the reaction pathways, while x‐ray photoelectron spectroscopy (XPS) reveals characteristic chemical shifts that account for C–O–C formation and suggest Co···O coordination. This controllable oxygen‐based connectivity provides a versatile platform to tune structure and electronic properties in porphyrinoid‐based polymers.

Motor contributions to temporal prediction extend beyond periodic rhythms

Abstract The auditory system requires a reliable and rapid tracking of the temporal dynamics of sounds. While moving in sync with a rhythm can improve timing perception, most research has focused on isochronous rhythms, conflating periodicity with predictability. This study aimed to determine whether the benefits of auditory-motor synchronization extend to aperiodic rhythms with predictable temporal structures and to uncover the neural correlates associated with the motor-enhanced benefit in timing performance. Participants listened to periodic (isochronous) and aperiodic (tempo-changing) rhythms while electroencephalography (EEG) was recorded. They imagined the continuation of each rhythm for two beats and judged the timing of a final target sound while either tapping along or listening attentively. Results showed that participants could synchronize their movements across all rhythm types. However, movement differentially affected temporal judgment across rhythms. Tapping significantly improved timing accuracy for isochronous and decelerating rhythms, demonstrating that strict periodicity is not a prerequisite for motor benefits. However, tapping impaired performance for accelerating rhythms. Behavioral evidence, supported by ERP findings, suggests that movement-induced delayed expectations during acceleration may override the predictive benefits of motor alignment. Thus, while the motor system supports general predictive processing beyond periodicity, accelerations and decelerations involve distinct predictive and motor processing demands.

Physiologically Robust Ultralong Aqueous Phosphorescence With Quantitative Hypoxia Sensing Through Hydrophobic‐Hydrophilic Engineering

ABSTRACT Organic room‐temperature phosphorescence (RTP) materials hold great promise as bioimaging agents due to their long‐lived emission and high signal‐to‐background ratios. However, their application in physiological environments is often hampered by water‐induced quenching. Herein, we report a ternary‐component nanoengineering strategy featuring a precisely engineered hydrophobic–hydrophilic architecture that enables bright, color‐tunable, and long‐lived RTP in aqueous media. The optimized 1,2‑PhCS@PLA nanoparticles achieve an ultralong phosphorescence lifetime of 1.04 s, the longest reported for aqueous organic RTP systems to date, and retain robust afterglow under physiological conditions with persistent RTP exceeding 12 s at 310 K (close to body temperature). This outstanding performance is enabled by a multifunctional hydrophobic layer that (1) protects triplet excitons from water, (2) suppresses nonradiative decay through matrix rigidity, and (3) allows dynamic oxygen responsiveness via its porous nature. These features enable quantitative in vitro hypoxia detection and high‐contrast afterglow imaging of tumor hypoxia in living mice, achieving a signal‐to‐background ratio up to 221. This work establishes a foundation for advanced phosphorescent biosensors and biomedical imaging applications.

A semi-public dynamic pre-matching model based on multi-head self-attention and temporal convolutional network for ship material procurement

Electricity‐Driven Radical Carbonyl Catalysis for Asymmetric Synthesis of <i>α</i> ‐Tertiary Amino Esters

ABSTRACT Electrochemistry has become a powerful and environmentally sustainable tool for driving redox transformations in modern chemical synthesis. However, achieving stereocontrol in electrocatalysis remains a persistent challenge. Introducing asymmetric organocatalysis into electrosynthesis offers an attractive strategy for controlling enantioselectivity, though successful systems to date are very limited. This limitation largely stems from several key factors, including the highly polar electrochemical environment, which can weaken noncovalent interactions, and the transient, highly reactive nature of radical intermediates, both of which complicate enantiocontrol. Employing chiral pyridoxal as a catalyst, we have successfully developed a novel asymmetric electrocatalytic system. This system facilitates an electricity‐driven, asymmetric oxidative coupling of amino acid esters with silyl enol ethers through radical carbonyl catalysis. The method enables the efficient synthesis of biologically significant α‐tertiary amino acid esters with good yields and excellent stereoselectivities. Beyond efficiently activating the amino acid esters, the chiral pyridoxal catalyst also delivers exceptional enantiocontrol even under highly polar reaction conditions, establishing an efficient organocatalytic platform for asymmetric electrosynthesis.

Patient awareness of viral hepatitis infection in Al-Madinah, Saudi Arabia: a cross-sectional study

Water, Alcohols, Amines, and Amides as Formal Hydrogen‐Atom‐Transfer Reagents Through Activation With Redox‐Active Lewis Acids

ABSTRACT The O─H and N─H bonds of protic molecules such as water, alcohols, amines, or amides typically resist hydrogen‐atom abstraction because of the high energy of the resulting heteroatom‐centered radical intermediates. However, association of the protic molecules with redox‐active Lewis acids provides stabilization of the generated reactive radical intermediates and enables the ligated protic molecules to serve as hydrogen‐atom donors or proton‐coupled‐electron‐transfer reagents. This review presents an overview of applications of this bond‐weakening principle in organic synthesis and attempts to illustrate the breadth of systems that enable such reactivity.

Predictors of infant mortality in a population-based surveillance cohort: the role of high-risk pregnancies and rare-event modelling

Tuning Water Transport in Subnanometer‐Sized Artificial Water Channels

ABSTRACT Water transport through nanochannels is not only essential for biological functions but also holds promise for the development of advanced flow sensors and membranes. In this study, a series of artificial water channels with subnanometer‐sized pores and tunable hydrophilicity were designed by mimicking the architecture of natural water channels. Experimental measurements and molecular dynamics (MD) simulations reveal that water transport can be modulated by pore hydrophilicity and electric field. Increasing pore hydrophilicity is associated with enhanced water permeability, consistent with continuous wetting and more uniform dipole alignment within the single‐file water wires. In contrast, a hydrophobic backbone impedes water transport due to dewetting effects and broader dipole orientation distributions. In addition, a static electric field significantly facilitates water transport and leads to a membrane polarization‐dependent water transport behavior by promoting more ordered water dipole configurations. These findings provide molecular‐level and external‐field‐based strategies to regulate water transport in subnanometer channels and may guide the design of energy‐efficient desalination membranes.

A two-stage deep learning framework for oil palm fresh fruit bunch ripeness classification toward predictive harvesting in precision agriculture

CO ₂ ‐to‐CO Electrochemical Conversion With an Fe(I) Porphyrin Complex in Water

ABSTRACT Iron porphyrin complexes constitute a well‐established and versatile class of molecular electrocatalysts for the reduction of CO 2 to CO. In both organic and aqueous media, the reaction mechanism is typically proposed to involve the interaction of CO 2 with a formally defined [(porphyrin)Fe 0 ] intermediate. In this work, we performed a mechanistic investigation of CO 2 reduction using the water‐soluble complex [( p TMA)Fe III Cl]Cl 4 under aqueous conditions. In situ scanning spectroelectrochemistry was employed, enabling the synchronized acquisition of UV–vis or IR spectra during cyclic voltammetry experiments. Our results provide strong evidence for CO 2 binding to the electrogenerated [( p TMA)Fe I ] 3+ species, followed by reductive C─O bond cleavage to yield a stable [( p TMA)(Cl)Fe II ‐CO] 3 + complex. This process corresponds to an overall two‐electron reduction per iron center. This mechanism, which has not been previously considered for molecular iron porphyrins in CO 2 reduction, is proposed to be facilitated by the charged porphyrin periphery and the hydrogen‐bonding network of the aqueous medium. These features may open new avenues toward achieving CO 2 reduction at lower overpotentials in water.

Eco-friendly synthesis of silver nanoparticles with dual metal sensing and antimicrobial potentials

An ELISA‐Inspired Self‐Propagating Click‐Fluoresce‐and‐Release Assay for the Ultrasensitive Detection of CD13 in Lung Cancer Patient Plasma

ABSTRACT Reaction‐based fluorescent probes often suffer from limited sensitivity in biomarker detection due to slow reaction kinetics and inherent stoichiometric constraints. Inspired by the decoupling of capture and detection in the enzyme‐linked immunosorbent assay (ELISA), we developed a click fluoresce and release (CFR) system, which is a two‐step detection platform comprising a capture probe and a detection probe. The capture probe converts the detection of an enzyme biomarker into the detection of tetrazine, which is then specifically recognized by the detection probe through a fluorogenic click reaction. Importantly, this click reaction simultaneously regenerates a molecule of tetrazine, establishing a self‐propagating cycle for signal amplification. CFR demonstrates superior detection limits and enhanced ability to discriminate low biomarker levels compared to conventional reaction‐based fluorescent probes, as validated by ultrasensitive detection of CD13 in complex biofluids. Notably, with this strategy, we found that plasma CD13 levels are significantly elevated in advanced lung cancer patients compared with early‐stage patients and healthy participants. Given its modular design, CFR can be readily adapted for the sensitive detection of various biomarkers by simply replacing the capture probe.

Low-complexity invasive weed optimization-assisted PTS and SLM framework for PAPR reduction in NOMA systems over fading channels

Key Drivers of Activity and Selectivity in Cu‐Based Catalysts for Methanol Synthesis From CO ₂ : Insights From Atomically Dispersed Promoters

ABSTRACT The synergistic Cu–metal oxide (Cu–MO x ) interface is critical for selective CO 2 hydrogenation to methanol, yet its mechanistic function, the central, long‐debated feature of industrial Cu/ZnO/Al 2 O 3 , remains ambiguous. Using operando transient DRIFTS‐SSITKA, we elucidate the roles of M + sites (Zn 2+ , Ga 3+ , and In 3+ ) on model Cu─M/SiO 2 catalysts prepared by surface organometallic chemistry (SOMC). X‐ray absorption spectroscopy reveals that these promoters restructure from alloys after reduction to cationic species at the interface under reaction conditions. We find the promoter's electronic effect on formate bond strengths provides quantitative descriptors for both activity and selectivity. All catalysts follow a common formate spillover mechanism, with methoxy hydrogenation/desorption as the rate‐limiting step. The intrinsic CH 3 OH formation rate follows a Sabatier‐type volcano with C─O bond strength, while selectivity correlates linearly with C─H bond strength (a proxy for the formate decomposition barrier). Cu─Ga/SiO 2 shows the fastest spillover, suppressing CO formation and yielding the highest selectivity; Cu─Zn/SiO 2 has optimal binding for the highest activity; In 3+ binds formate too strongly, creating a kinetic trap on the strong‐binding side of the volcano. These findings bring mechanistic clarity to the debated Cu─Zn(O) synergy, showing selectivity is governed by a balance of electronic stabilization and spillover dynamics.

Microbial spectrum and antimicrobial resistance are associated with outcomes after endoscopic ultrasound-guided therapy of pancreatic fluid collections

Abstract Infected pancreatic fluid collections (PFC) are among the most challenging entities in therapeutic endoscopy, requiring multiple interventions. In this multicenter study, we investigated whether microbiological profiles and antimicrobial resistance are associated with outcomes after endoscopic ultrasound-guided drainage. The primary endpoint was time to clinical success, defined as radiographic resolution of the PFC to &lt; 30 mm, no need for additional intervention, and clinical improvement. Secondary outcomes included surgery-free survival, number of interventions, and ICU stay. Among 398 included patients (median age: 56.5 years; 70.6% male), 232 (58.3%) had microbiologically confirmed infection. Complete resolution was achieved in 89.2% of infected PFCs (median: 70 days; IQR 37–118) versus 95.2% of sterile PFCs (57 days; IQR 33–91). Resolution was significantly delayed in Enterococcus ( n  = 107; 26.9%) and polymicrobial resistant infections ( n  = 38; 9.5%): 87 days ( p  = 0.003) and 120 days ( p  &lt; 0.001), respectively. Enterococcus species remained an independent predictor in multivariable Cox regression, and in a sensitivity analysis restricted to the necrosectomy group (aHR 2.50; p  = 0.002). Vancomycin-resistant Enterococcus (VRE) infection ( n  = 26; 6.5%) was associated with the highest number of interventions (median: 6), longest ICU stays (median: 72 days), and highest mortality (23%). In summary, this study identifies an association of Enterococcus species and antimicrobial resistance with poor outcomes after EUS-guided therapy, emphasizing the importance of microbiology-informed treatment strategies.