Browse Articles

First Evidence for Ozonido‐TMC Complexes of Iron and Cobalt

ABSTRACT We present compelling evidence for the first Fe‐ and Co‐ozonido complexes: [(D 12 ‐TMC)Fe III (O 3 )(OTf)](B Ar F), [(D 12 ‐TMC)Fe III (O 3 )(I)](B Ar F), and {[(D 12 ‐TMC)Co III (F)] 2 (O 3 )}(B Ar F) 2 from the reactions of complexes [(D 12 ‐TMC)Fe II ( X )]B Ar F and [(D 12 ‐TMC)Co II ( X )]B Ar F ( X   =  OTf, F, I) with ozone in 2‐Me‐THF/THF solutions using ultraviolet–visible spectroscopic and cryospray mass spectrometric techniques at cryogenic temperatures as low as −155°C (118 K). Further reactivity studies suggest the subsequent formation of Fe‐ and Co‐oxido complexes [(D 12 ‐TMC)Fe IV (O)(OTf)]B Ar F, [(D 12 ‐TMC)Co IV (O)(OTf)]B Ar F, and [(D 12 ‐TMC)Co IV (O)(F)]B Ar F. Density functional theory computations with the ω B97X‐3c three‐component method and the ω B97X‐D4 hybrid functional corroborate our spectroscopic results. Further key results of our studies entail the synthesis of several hitherto unreported Fe and Co complexes, including complexes with strongly (F) and moderately stabilizing (OTf) anions without extraneous coordinated solvent molecules. The D 12 ‐TMC ligand proves to be effective for preventing methyl group hydroxylation as observed, for example, in the case of [(TMCO)Co III (H 2 O)](OTf) 2 . With ozonide [N(CH 3 ) 4 ]O 3 , we instead obtained crystals of [(D 12 ‐TMC‐propyl‐O)Co III (OTf)]B Ar F from [(D 12 ‐TMC)Co II (OTf)]B Ar F. The generation of these transient Fe‐ and Co‐complexes demonstrates that temperatures below values attainable by typical stopped‐flow setups in conjunction with “ligand hardening” provide a promising strategy for studies of reactive complexes.

Machine learning-based forecasting of CO2-related economic growth and agricultural land change in IORA countries

Manipulating Interfacial Water Molecules via Eutectic‐Polymer Dual‐Network for Stable Electrochromic Devices

ABSTRACT Aqueous Zn‐WO 3 electrochromic devices (ZWEDs) represent a promising frontier in energy‐efficient electrochromic systems. However, their practical application is hindered by the short device lifespans due to the poor electrode/electrolyte interfacial stability which originates from high water activity. Herein, we develop a eutectic‐polymer dual‐network electrolyte to regulate water activity and stabilize the electrode/electrolyte interface. Combined in situ/ex situ spectroscopic analysis and simulations reveal that this eutectic‐polymer dual‐network stabilize the electrode structure via two complementary effects: (i) reconstruction of the hydrogen‐bond network confines free water molecules, suppressing water activity and parasitic reactions; and (ii) preferential adsorption of acetamide molecules over water on the electrode surfaces forms a stable molecular interfacial layer that regulates Zn 2+ electrochemical behavior and further mitigates water‐induced side reactions. Benefiting from the synergy between hydrogen‐bond reconstruction and interfacial adsorption, the interfacial stabilities of both Zn anode and WO 3 cathode are significantly enhanced. Consequently, the Zn‐WO 3 device achieves outstanding cyclic stability in both ion storage and optical modulation over 1000 cycles, with an operational temperature range expanded to −30°C∼80°C. This strategy offers a promising pathway to enhance the interfacial stability in ZWEDs across a wide temperature range.

Charge based boundary element method with residual driven adaptive mesh refinement for high resolution electrical stimulation modeling

Subcellular Tandem‐Activated Signal Amplification for Spatially Precise Molecular Imaging in Mitochondria

ABSTRACT Despite significant advances in DNA‐based signal amplification strategies for sensitive molecular imaging in live cells, achieving subcellular resolution remains challenging due to limited spatial precision. Here, we present a subcellular tandem‐regulated, spatially selective signal amplification technology for molecular imaging in mitochondria. This platform integrates ribosomal RNA (rRNA)‐activated target‐aptamer recognition with enzyme‐mediated cascade signal amplification, enabling in situ imaging of ATP within defined subcellular compartments (e.g., mitochondria) or membraneless regions (e.g., cytosol). The system facilitates in situ monitoring of ATP dynamics during drug intervention with enhanced spatial precision and sensitivity. Furthermore, by re‐engineering the cascade‐regulated sensor, we extended this approach to enable correlated imaging of mitochondrial ATP and microRNA. This strategy offers a powerful, modular tool for probing energy metabolism and regulatory networks across different subcellular environments.

Enzymatic and chemical glycosylation of sugarcane-derived sucrose yields glycosides with moderate anti-inflammatory activity in vitro

Abstract Chronic inflammation is a key driver of many non-communicable diseases, yet current pharmacological therapies are often limited by adverse effects and poor accessibility. Engineered sucrose-derived glycosides from sugarcane offer a sustainable, food-derived candidate with the potential to modulate inflammatory pathways safely and effectively. We developed a dual synthetic approach combining enzymatic and acid-catalyzed glycosylation to generate targeted glycosides. Products were purified and characterized using HPLC, LC-MS, and NMR, achieving high yields and analytical reproducibility. Anti-inflammatory efficacy was evaluated in LPS-stimulated THP-1 macrophages via cytokine assays, while bioavailability was assessed using Caco-2 monolayers. Stability testing in simulated gastric and intestinal fluids and cytotoxicity profiling were also performed. All experiments were conducted in triplicate and analyzed using one-way ANOVA with Tukey’s post hoc test. All glycosides demonstrated high yields (84.9–86.4%), significant cytokine suppression (TNF-α: −35.2% ± 1.8%; IL-6: −33.1% ± 1.5%; p  < 0.001), and favorable permeability (2.3–2.5 × 10⁻⁶ cm/s) with > 90% stability under gastrointestinal conditions. No cytotoxicity was observed up to 200 µM. While sucrose-derived glycosides have been reported in related literature to influence NF-κB and MAPK signaling, the present study did not directly evaluate these pathways. Therefore, any mechanistic interpretation remains hypothetical and requires targeted validation. This is the first integrated demonstration of scalable, high-purity, sugarcane-derived glycosides with moderate but statistically significant in vitro anti-inflammatory activity, measurable intestinal permeability in the Caco-2 model, and food-grade stability. These findings support their development as next-generation nutraceuticals, supporting further investigation toward food-grade applications.

Iminodiacetate Chelated Zinc Complex Electrolyte Enables High‐Voltage and Long‐Life Zinc‐Based Flow Batteries

ABSTRACT Conventionally, lowering the Zn plating/stripping potential relies on strongly alkaline electrolytes that convert Zn 2+ into zincate species. However, such conditions often exacerbate Zn corrosion and severe dendrite growth. Here, we introduce an iminodiacetate (IDA 2− )‐based coordination strategy that enables reversible Zn plating/stripping under mildly alkaline conditions (pH ∼12). The hexacoordinated [Zn(IDA) 2 ] 2− shifts the Zn plating/stripping potential to −1.17 V versus SHE. A demonstrated zinc‐iodine flow battery delivers a voltage of ∼1.7 V with a peak power density of 561.5 mW cm −2 and sustains cycling over 700 cycles at 100 mA cm −2 with Zn areal capacity of 90 mAh cm −2 . This strategy is further validated in a zinc‐iron redox flow battery, achieving an operating voltage of ∼1.6 V with average Coulombic efficiency of 99.3% over 750 cycles. Collectively, these results suggest that the proposed coordination chemistry offers a promising avenue toward the development of high‐voltage long‐life zinc‐based redox flow batteries.

Trajectories of anxiety and depressive symptoms during hospitalization for hematopoietic stem cell transplantation

Oo oo, ha ha: why humans and great apes giggle alike when tickled

A Quantitative Electrostatic Potential Descriptor Enables Deep Learning‐Accelerated Discovery of High‐Performance Lithium‐Ion Battery Electrolytes

ABSTRACT Rational electrolyte design for high‐energy‐density lithium‐ion batteries (LIBs) urgently demands precise and quantitative molecular descriptors of solvation power to enable deep learning (DL)‐accelerated screening, yet such descriptors remain lacking. Here, we introduce the electrostatic potential ratio |ESP min |/ESP max (ESP ratio ) as a quantitative descriptor capturing the balance between electron‐donating and electron‐accepting capacities, and identify a solvation modulation zone (0.9 < ESP ratio  < 2.4) through unsupervised clustering of 344 molecules encompassing 196 experimentally reported LIB electrolyte molecules. By combining this descriptor with self‐supervised pre‐trained DL models fine‐tuned on small experimental datasets, we enable hierarchical screening of ∼10 6 PubChem molecules and prioritize electrolyte candidates from previously unexplored chemical space. Experimental evaluation of representative candidates, including TBDN and PIV as co‐solvents and additional nitrile‐containing molecules as electrolyte additives, confirms that the ESP ratio ‐guided workflow can enrich chemically meaningful electrolyte candidates for high‐voltage Li||LiCoO 2 .

A novel reflective intelligence optimizer with machine learning (RIO-ML) for parameter estimation of photovoltaic models

Abstract This paper presents a new Reflective Intelligence Optimizer with Machine Learning (RIO-ML) approach to estimate the parameters of solar photovoltaic (PV) equivalent circuit models, which are highly nonlinear and multimodal, and hence require efficient handling by conventional optimizers. RIO-ML combines three major components: a multi-leader social learning algorithm with personal-best reflective memory, machine learning-driven adaptive control of important parameters using Multi-Layer Perceptron models, and progressive Gaussian refinement with reflective boundary treatment for improved convergence and robustness. The performance of RIO-ML is tested on the standard RTC France solar cell model with three different model settings: Single Diode Model (SDM) with 5 parameters, Double Diode Model (DDM) with 7 parameters, and Triple Diode Model (TDM) with 9 parameters, for 30 independent runs for each scenario. RIO-ML obtains the minimum RMSE of 8.739710 × 10 − 4 A, 8.456760 × 10 − 4 , and 7.7546980 × 10 − 4 A for SDM, DDM, and TDM models, respectively, with corresponding low mean RMSE values of 2.223109 × 10 − 3 A, 2.282687 × 10 − 3 A, and 1.717649 × 10 − 3 A. Comparative studies reveal that RIO-ML performs better than some of the best metaheuristic algorithms available in the literature with respect to solution quality, convergence rate, and robustness, while maintaining the maximum absolute current errors less than 1.6 × 10 − 3 A for all models. These findings clearly indicate that the developed RIO-ML approach is an effective and efficient tool for accurate estimation of PV parameter values.

Electropolymerized Donor–Acceptor Cathodes for Photoresponsive Li‐Dual‐Ion Batteries

ABSTRACT As a novel energy storage method, photo‐assisted rechargeable batteries offer an effective solution to numerous issues currently plaguing organic lithium‐ion batteries. Herein, we propose two donor–acceptor (D–A) structure‐based organic bifunctional electrode materials (TPA‐PTO and CZ‐PTO), which integrates photocatalysis and redox activity. The electropolymerization of D–A conjugated polymer extends π‐conjugation, reduces the molecular bandgap, broadens the light absorption spectrum, and improves intramolecular electron transfer. Specifically, the long exciton lifetimes enable efficient photo‐exciton charge separation and directional charge transfer. Under light irradiation, the photo‐electrodes achieved a capacity of 232 mAh g −1 at 0.2 A g −1 , while the impedance decreased by 50%. Furthermore, the photo‐assisted cell demonstrates remarkable 55% increased capacity at high current density of 10 A g −1 . The exciton transfer dynamic mechanisms of photo‐assisted dual‐ion batteries were also demonstrated by examining the differential effects of light exposure on anion and cation intercalation.

Circulating carbohydrate antigen Ca10H predicts favorable prognosis in colorectal cancer

Kai S. Exner

A theoretical analysis of PhysioChem-K-mer features for protein classification using controlled synthetic benchmarks

Abstract Standard k-mer methods treat amino acids as categorical tokens without directly encoding physicochemical properties. Although physicochemical properties have been incorporated into various bioinformatics tasks, their potential as a direct, systematic alternative for the k-mer counting paradigm has not been fully evaluated. We present PhysioChem-K-mer, a framework that transforms protein sequences into physicochemical property-based feature spaces, serving as an alternative to conventional amino-acid-identity k-mer representations. Our main hypothesis is that property-based representations capture functional constraints more effectively than traditional amino acid-based methods. To test this hypothesis, we created a controlled benchmark comprising 1500 synthetic sequences spanning 10 diverse protein families. The dataset retained core functional motifs while deliberately excluding evolutionary patterns typically found in natural biological sequences. Notably, our hydropathy-based PhysioChem-K-mer achieved a classification accuracy of 81.33% on a controlled synthetic benchmark, representing an absolute gain of 44.33% points over standard 3-mer methods (37.00%). The framework was further evaluated using real UniProt/Swiss-Prot data, comprising 11,620 sequences across 10 families, to ensure practical generalizability. Based on real data, PhysioChem-Hydropathy achieved 64.63%, an absolute gain of 47.68% points over the standard 3-mer baseline (16.95%), while reducing features by 73.9% and training time by 81.6%. By directly integrating biochemical knowledge into feature representations as a primary design principle, PhysioChem-K-mer combines interpretability with computational efficiency. These results suggest that physicochemical properties offer a vital source of information for protein classification, validated here on both synthetic and real-world data.

A Cellulose‐Derived Polymer Additive for Stabilizing Thick Cathodes in All‐Solid‐State Batteries

ABSTRACT All‐solid‐state batteries (ASSBs) offer enhanced safety and energy density over conventional lithium‐ion batteries. However, achieving high active material loading remains challenging due to poor interfacial contact from cold‐pressing and the incompatibility of solvent‐based processing with advanced solid‐state electrolytes. Herein, we report a cellulose‐derived polymer additive (CA‐MDI) that establishes intimate solid–solid interfacial contact while ensuring continuous electron/ion transport in the composite cathodes. The efficacy of CA‐MDI is ascribed to the urethane‐linked cellulose framework, which is synthesized via the polymerization of cellulose acetate (CA) and methylene diphenyl diisocyanate (MDI). The as‐constructed ASSBs incorporating a CA‐MDI‐modified LiNi 0.89 Co 0.055 Mn 0.055 O 2 cathode achieve a high areal capacity of 6.4 mAh cm −2 , delivering an initial discharge capacity of 136.6 mAh g −1 at 0.3C and retaining 91.1% of the capacity after 100 cycles, whereas additive‐free cells show rapid degradation. At a lower areal capacity of 1.8 mAh cm −2 , the CA‐MDI‐modified cell maintains 80% of its initial capacity for over 620 cycles at 1 C. The applicability of the CA‐MDI additive is further demonstrated using LiCoO 2 and Li‐rich layered oxide cathodes. These results show that a mechanically adaptive polymer additive can improve the cycling stability of thick composite cathodes and provide a useful approach for developing high‐energy‐density ASSBs.

Experimental evidence of male–male interaction in laboratory swarms of Anopheles gambiae mosquitoes

Abstract Mosquitoes mostly mate in the context of swarms: to facilitate encounters with females, males form disordered aggregations over a visual marker, which serves as a positional reference. While the relevance of this visual marker for swarming activity has been largely addressed, it is still poorly understood whether, in addition to an individual’s response to environmental stimuli, insects in a swarm interact with each other, giving rise to a collective behavior. Here, with a dataset comprising three-dimensional trajectories of 30 laboratory swarms of different sizes (ranging from 80 to 400 mosquitoes), we investigate swarming behavior of Anopheles gambiae mosquitoes. We find that individual speed fluctuations are strongly correlated in space, meaning that mosquitoes in close proximity tend to display similar deviations from the group average, effectively flying at a similar speed, although no such correlation is observed in the flight direction. With a series of targeted tests, we prove that this correlation is not compatible with a random arrangement of individuals, nor with random fluctuations of individual speeds, thereby providing empirical evidence of an effective male-male interaction at play in our swarms.

Tetraborylated Multiple Resonance Emitter Incorporating B─O Bond‐Embedded π‐Extension for Ultra‐Narrowband and High‐Efficiency Blue Devices

ABSTRACT Ultra‐narrowband multiple resonance (MR) thermally activated delayed fluorescence (MR‐TADF) emitters are crucial for next‐generation ultra‐high‐definition full‐color displays. However, current blue MR‐TADF emitters still face significant challenges in simultaneously achieving ultra‐narrowband emission, high quantum efficiency, and a fast reverse intersystem crossing (RISC) rate ( k RISC ). Herein, we propose a boron–oxygen (B─O) bond‐embedded design strategy and develop a nanographene‐based MR‐TADF molecule containing 17‐fused rings. This tetraboron compound, 4B4N2O, exhibits ultra‐narrow blue emission in n ‐hexane solution with an emission peak at 461 nm and a full width at half maximum (FWHM) of only 11 nm. Benefiting from its high photoluminescence quantum yield (PLQY = 99%), high horizontal dipole ratio ( Θ // = 93%), and fast k RISC (5.32 × 10 5 s −1 ), the corresponding device achieves an excellent external quantum efficiency (EQE) of 40.3% and low efficiency roll‐off (EQE 1000 = 31.4%). Moreover, the device exhibits an ultra‐narrow electroluminescence (EL) FWHM of 16 nm and CIE coordinates of (0.11, 0.18). The ultra‐narrowband tetraboron emitter presented herein holds great promise for enabling next‐generation energy‐saving ultra‐high‐definition displays and AR/VR technologies.

Trimester-specific reference intervals for coagulation biomarkers (TAT, PIC, TM, tPAI-C) and their clinical associations in healthy Chinese pregnant women

Toward the Synthesis of Pestalustaine A: Structural Revision and Formation of Original Strained Tricyclic Architectures

ABSTRACT We report our quest toward the total synthesis of the reported structure of the sesquiterpene pestalustaine A and its unprecedented tricyclic skeleton. Our retrosynthesis involved a transannular Michael addition of a 1,3‐keto‐ester and enal‐containing bicyclo[4.4.1]undec‐3‐ene obtained from the ring expansion of a chiral γ,γ−disubstituted cyclohexanone and stereoselective Hosomi‐Sakurai reaction. Serendipity allowed us to uncover powerful divergent and unexpected cyclizations of this bicycle in ionic or oxidative conditions, giving access to complex tricyclic architectures such as tricyclo[5.2.1.1 2,5 ]undecane, octahydro‐1,5‐methanonaphthalene, octahydro‐12,6‐methanonaphthalene frameworks, and the octahydro‐1,5‐methanoazulene reported skeleton of pestalustaine A. The present synthetic study also led us to note a discrepancy between the reported structure of pestalustaine A and the 2D NMR data, which led us to propose a revised structure of the natural product to a caryophyllene‐type framework, a reassignment supported by computational prediction of NMR chemical shifts.