Browse Articles

Tissue-specific and sex-biased glycoproteomic landscape of Schistosoma mansoni

<i>Cis‐Trans</i> Isomerism Revealed in Circularly Polarized Luminescent Superatomic Ag ₂₈ Nanoclusters

Abstract Atomically precise metal nanoclusters facilitate the exploration of chiral origin in metal nanomaterials, meanwhile, their structural isomers with subtle variations serve as ideal models for investigating the structure‐property relationship at the atomic level. Here, we obtained two pairs of chiral superatomic cis ‐ trans isomers with the formula [ R/S ‐Ag 28 (SOC 10 H 15 ) 14 (CF 3 COO) 10 ] (denoted as R/S ‐Ag 28 ‐ cis/trans ), where the cis and trans configurations coexist within the R and S chiral forms, respectively. Single crystal X‐ray diffraction (SCXRD) analysis revealed that Ag 28 clusters adopt a chiral core‐shell configuration of Ag 12 @Ag 14 S 12 , consisting of an Ag 12 kernel encapsulated within a chiral Ag 14 S 12 cage. The additional two AgS units are located in a different fashion on the flanks of the framework, leading to the cis ‐ trans isomerism of the silver clusters. DFT calculation reveals the distinctions in electronic structures and optical absorptions of the cis ‐ trans isomers. The enantiomeric R/S ‐Ag 28 exhibit intense red phosphorescence at 740 nm in the crystalline state, and hold a ∼28 nm blueshift in solution. Furthermore, R/S ‐Ag 28 display circularly polarized luminescence (CPL) activity, achieving a maximum (| g lum |) value of 1 × 10 −3 in the crystalline state. This study enriches the diversity of chiral superatomic clusters and introduces cis ‐ trans isomerism in metal clusters, establishing a novel platform to explore structure‐activity relationships.

Unveiling the metallogenic continuum of an Archean craton

Reentrant melting of scarred odd crystals by self-shear

Abstract Spatial confinement can induce geometrical frustration in condensed phases, giving rise to topological defects that confer materials with new and exotic properties. Here, we experimentally uncover the effect of confinement-induced defect strings termed ‘grain boundary scars’ on the behavior of dense two-dimensional assemblies of granular spinners, a canonical odd elastic solid. The spatial arrangement of these scars fundamentally reshapes the flows triggered by chiral activity. Specifically, they cause the topologically protected edge flows - a ubiquitous feature of confined spinner assemblies - to decouple from the bulk. Strikingly, increasing the net chiral activity of the system by tuning the ratio of counterclockwise to clockwise spinners caused spontaneous self-shearing. The resulting odd radial stresses led to a chiral activity-mediated reentrant melting transition at a fixed areal spinner density. Our findings open new avenues for exploiting geometrical frustration to elicit novel responses from odd elastic solids.

Phosphine‐Catalyzed Enantioselective [2 + 2] Annulations of <i>α</i> ‐Allyl <i>γ</i> ‐Benzyl Allenoates via a Transannular Cyclization Approach

Abstract Fused cyclobutane frameworks are valuable scaffolds in natural products and pharmaceuticals, yet catalytic asymmetric methods for their construction remain rare due to ring strain and stereocontrol challenges. Here, we report a spiro phosphine‐catalyzed, stereoconvergent, and enantioselective [2 + 2] annulation of racemic α ‐allyl γ ‐benzyl allenoates via transannular cyclization, efficiently delivering bicyclo[3.2.0]heptenes in high yields and excellent enantioselectivity. Experimental studies and DFT calculations indicate a stepwise mechanism involving seven‐membered zwitterion formation, dynamic kinetic resolution through reversible nucleophilic addition, and a rate‐ and enantioselectivity‐determining deprotonation via intramolecular hydrogen transfer. This protocol offers a concise and general approach to enantioenriched fused cyclobutanes, expanding synthetic options for drug discovery.

Unlocking Hydrogen‐Bond Network‐Mediated Directional Spillover Mechanism in Electrocatalytic Hydrogen Evolution

Abstract Hydrogen spillover offers a promising route to circumvent scaling relations in the electrocatalytic hydrogen evolution reaction (HER) by spatially decoupling the hydrogen adsorption and desorption steps. However, its practical application has been limited by sluggish spillover kinetics across heterogeneous interfaces. In this work, we propose a hydrogen‐bond (H‐bond) network‐mediated spillover mechanism that bypasses conventional interfacial mediation. Within this mechanism, active hydrogen species (H*) generated on one component sequentially enter the H‐bond network, undergo directional transport via Grotthuss‐type H* hopping along the network, and ultimately uptake onto another component. To realize this concept, we designed a Pt/g‐C 3 N 4 /CoP catalyst, in which Pt effectively enriches H* to establish a coverage gradient from Pt→g‐C 3 N 4 →CoP; g‐C 3 N 4 optimizes the proximity of the H‐bond network to facilitate H* shuttling and serves as H* relay sites; and CoP provides facile sites for H 2 desorption. This configuration enables efficient H‐bond network‐mediated spillover along the Pt→g‐C 3 N 4 →CoP pathway, achieving an ultrahigh Pt‐mass‐normalized HER activity of 175.0 A mg Pt −1 at −0.1 V vs. RHE in acidic medium. The mechanism elucidated here opens new avenues for catalyst design in multi‐step hydrogen‐involving electrocatalytic processes.

Improving erectile function in diabetic male mice by rescuing depalmitoylated FBP1 to reduce cavernosal lactate

Adipocytic sclerostin loop3-LRP4 interaction required by sclerostin to impair whole-body lipid and glucose metabolism

Abstract Sclerostin, which has three loops, inhibits bone formation and impairs whole-body lipid and glucose metabolism. The marketed therapeutic sclerostin antibody for postmenopausal osteoporosis (POP) mainly targeting loop2 promotes bone formation and improves whole-body lipid and glucose metabolism. However, FDA/EMA warns of its cardiovascular risk. We previously demonstrate that sclerostin loop3 contributes to the inhibitory effect of sclerostin on bone formation but not its cardioprotective effect. Here we find elevated serum sclerostin levels in both POP-T2DM patients and newly-diagnosed T2DM patients and further demonstrate that sclerostin loop3 participates in the impairment effect of sclerostin on whole-body lipid and glucose metabolism in vivo. Mechanistically, specific blockade of adipocytic sclerostin loop3-LRP4 interaction attenuates the impairment effect of sclerostin on lipid and glucose metabolism in vitro and in vivo. This study provides an innovative strategy, blocking adipocytic sclerostin loop3-LRP4 interaction, to normalize lipid and glucose metabolism in POP-T2DM patients, in cardiovascular safety.

Patient-reported health utility of stroke and gastrointestinal bleeding related to DOACs in atrial fibrillation: a vignette-based substudy of a randomized controlled trial

Electrochemical Azolation of Electron‐rich Fluoroarenes: A Controlled Redox Chain Unlocks C─N Bond‐forming <i>e</i> ‐S _N Ar

Abstract Nucleophilic aromatic substitution (S N Ar) reactions are critical methods for forming C─N bonds in synthetic campaigns, but limitations in electrophile electronics restrict access to a large portion of chemical space. Photochemical oxidation of fluoroarenes has emerged as an attractive strategy to activate fluoroarenes toward nucleophilic addition, but back‐electron transfer to solution‐phase reduced photocatalysts limit the scope and efficiency of these methods. Herein, we describe an electrochemical strategy to overcome this obstacle by spatially separating redox events at electrode surfaces, extending the lifetime of the activated electrophile and enabling the azolation of electron‐rich alkoxyfluoroarenes. Through stabilization of the oxidized product with voltage control and HFIP solvent, the reaction proceeds with catalytic charge via a proposed uphill redox chain mechanism. A wide range of electron‐rich fluoroarenes and azoles are tolerated—including those with orthogonal functional group handles. The redox catalytic nature of this e ‐S N Ar reaction enables energy and mass efficient syntheses and facile scaling in a simple batch setup.

Reticulating node-linker-modulator chemical spaces for modular design of alkoxide-based glasses and liquids

The peak shifting electricity consumption management and influencing factors of smart grid from recurrent neural network model and deep learning

First‐Order Phase Transformation in Highly Concentrated Electrolyte for High‐Rate and Long‐Cycle Aqueous Zn‐Ion Battery

Abstract Concentrated electrolyte offers a promising approach to enhance aqueous batteries, yet its influence on electrode phase transformations and mechanical properties remains largely unknown. This work shows that salt‐concentrated electrolyte induces a first‐order phase transformation, rather than the conventional conversion reaction of VS 4 cathode typically observed in dilute electrolyte. This transformation results in a semi‐coherent phase boundary, reducing strain and improving energy efficiency. As a result, capacity doubles and cycle life increase sixty‐fold compared to regular dilute electrolyte. The first‐order phase transformation is attributed to reduced de‐solvation energy and charge transfer energy barrier due to different Zn 2+ solvation structure in the concentrated electrolyte. Our findings offer groundbreaking insights into the microstructure evolution of electrode in concentrated electrolyte and pave the way to further develop batteries with excellent performance.

Systems acclimation to osmotic stress in zygnematophyte cells

Abstract Zygnematophytes are the closest algal relatives of land plants. They hold key information to infer how the earliest land plants overcame the barrage of terrestrial stressors, the prime of which is osmotic stress. Here, we apply two osmotic stressors on a unicellular and a multicellular representative of zygnematophytes and study their responses over a 25-hour time course, generating 130, 60, and 30 transcriptomic, proteomic, and metabolomic samples combined with photophysiology, sugar analysis, immunocytochemical glycoprotein analysis, and microscopy. Our data highlight a shared protein chassis that shows divergent responses with the same outcome: successful acclimation to osmotic challenges. We establish a model of how the algal sisters of land plants can overcome a prime stressor in the terrestrial habitat and highlight components of the plant terrestrialization toolkit.

Exploring the links between swimming performance, glucocorticoid profiles, behavioral types and cardiac morphology in migrating Atlantic salmon (Salmo salar) smolts

Abstract It has been become increasingly clear that swimming performance is crucial for the migratory success of wild Atlantic salmon ( Salmo salar ) smolts, yet the associated traits remain largely unexplored. In this study, smolts were caught during their downstream migration to the sea and were categorized as strong or poor swimmers based on their time to fatigue in a swimming test. Behavioral profiles were characterized through a confinement and novelty test, and relationships to cardiac morphology and glucocorticoid profiles were investigated. Strong swimmers increased activity over time in the confinement test, while poor swimmers showed the opposite trend, indicating differences in boldness. There were no differences in plasma cortisol in groups of fish with contrasting swimming performance. Still, strong swimmers had higher cortisone levels 24 h after the swim test, suggesting a protective mechanism against elevated cortisol in this group. No differences in heart morphology were found between the groups. In addition, acoustic telemetry revealed a trend toward lower survival rates for strong swimmers in predator-rich environments. Overall, our results highlight a link between glucocorticoid profiles, boldness and swimming capacity in Atlantic salmon smolts. Further studies are needed to confirm the observed survival patterns and to better understand how predator pressure may shape the fitness consequences of these traits in migrating smolts.

Physically Masked Nanoflares for Accurate Biological Applications by Blocking Nucleases

Abstract Nanoflare integrated with a gold nanoparticle (Au NP) core and a functional oligonucleotide shell is a powerful platform for bio‐applications, such as sensing, imaging, diagnosis, and therapy. However, degradation of nucleic acids by endogenous nucleases in vivo is an inevitable problem causing signal distortion. To solve this issue, in this work, a physically masked strategy was designed by trapping the nanoflare in a porous polymer nanocage. The porous structure of the nanocage allowed the penetration of small target molecules to react with the internal nanoflare, while bulky nucleases were blocked, resulting in high‐fidelity fluorescence signaling. Using this method, cancer cells were differentiated from normal cells by a masked nanoflare that can recognize a microRNA biomarker (miRNA‐21), and tumors were imaged with a high‐contrast signal. The physical masking strategy opened up a new path for improving the stability of nucleic acid probes against nucleases, facilitating accurate bio‐application.

Multiscale imaging on proton pump-driven acidity for assessing tumor progression and metastasis

In vitro effects of Bacillus velezensis strain Mandacaium against Xanthomonas citri pv. glycines: genomic and metabolomic insights

Polymerase mutations underlie early adaptation of H5N1 influenza virus to dairy cattle and other mammals

Abstract In 2024, an unprecedented outbreak of H5N1 high pathogenicity avian influenza was detected in dairy cattle in the USA resulting in spillbacks into poultry, wild birds and other mammals including humans. Here, we present molecular and virological evidence that the cattle B3.13 genotype H5N1 viruses rapidly accumulated adaptations in polymerase genes that enabled better replication in bovine cells and tissues, as well as cells of other mammals including humans. We find evidence of several mammalian adaptations in cattle including PB2 M631L, which is found in all cattle sequences, and PA K497R, which is found in the majority. Structurally, PB2 M631L maps to the polymerase-ANP32 interface, an essential host factor for viral genome replication. We show that this mutation adapts the polymerase to better interact with bovine ANP32 proteins, particularly ANP32A, and thereby enhances virus replication in bovine mammary systems and primary human airway cultures. We show that ongoing evolution in the PB2 gene, including E627K and a convergently arising D740N substitution, further increase polymerase activity and virus replication in a range of mammalian cells. Thus, circulation of H5N1 in dairy cattle allows virus adaption improving replicative ability in cattle and poses a continued risk of zoonotic spillover.

A hybrid learning framework integrating chaotic Niche alpha evolution for student academic performance prediction