Browse Articles

Rhodium‐Catalyzed Enantioselective Synthesis of Planar‐Chiral Macrocycles via De Novo Isoquinoline Formation

ABSTRACT De novo formation of the aromatic ring is an attractive strategy for atroposelective synthesis, but its application to planar‐chiral macrocycles remains challenging. Herein, we report a rhodium‐catalyzed enantioselective synthesis of planar‐chiral macrocycles via de novo isoquinoline construction. This method is characterized by high levels of enantioselectivity (up to 96% ee), regioselectivity (up to >20:1 rr), and functional group tolerance, providing a series of isoquinoline‐based macrocyclic atropisomers. Furthermore, the synthetic utility of this protocol is validated via a mmol‐scale reaction and post‐modification process of the product. Mechanistic studies, including deuterium labeling, kinetic isotope effect, and DFT calculations, support C─H bond cleavage as the rate‐determining step and elucidate the origin of the stereoselectivity.

A dual-function dry electrode for electromyography recording and transcutaneous electrical stimulation

Multi‐Scale Architecture Regulation of Hard Carbons for High‐Efficiency Sodium Storage Across Ambient and Subzero Conditions

ABSTRACT Hard carbons, despite their cost‐efficient production and precursor availability, face critical electrochemical performance constraints from excessive defects, limited closed‐pore structures, and poor interfacial stability. Herein, a multi‐scale structural regulation strategy is proposed to tailor both micro‐ and nanoscale architectures of polymer‐derived hard carbons for efficient sodium storage under both ambient and subzero conditions. The pitch‐modulated carbonization directs the self‐assembly of polyphosphazene (PZS) precursors into monodisperse microparticles while in situ forming nanoscale short‐range‐ordered graphitic domains. The resulting hard carbons integrate enhanced bulk conductivity, abundant closed pores, and defect‐tailored low‐surface‐area microparticles, collectively enabling an inorganic‐rich solid electrolyte interphase (SEI), fast Na + transport, and suppressed side reactions. The optimized sample delivers a remarkable reversible capacity (413.7 mAh g −1 at 0.05 A g −1 ) with high initial Columbic efficiency (ICE) (87.1%) and excellent rate capability. More notably, it demonstrates high reversible capacity and exceptional cycling stability at −20°C, achieving a remarkable capacity retention of 98.8% after 3000 cycles and highlighting its practical viability under extreme conditions. The sodium storage mechanisms and accelerated kinetics are revealed through various in situ characterizations and computational techniques, providing deep insights into microstructure tailoring of hard carbons for high‐performance sodium‐ion batteries (SIBs).

Comprehensive machine learning identifies anoikis signatures predicting therapeutic resistance and survival in gastric cancer

Structure, evolution, phylogeny, and analysis of domain-deficient genes in the IQD gene family of Brassica juncea

Abstract The plant IQD gene family plays crucial roles in abiotic stress response and plant growth regulation. However, the biological functions of IQD genes in Brassica juncea remain largely unknown. Here, we conducted biological analyses to identify and characterize the IQD gene family in B. juncea , providing new insights for future research on the IQD gene family. We identified 107 IQD genes in B. juncea , which are distributed across 18 chromosomes. Collinearity analysis reveals that segmental duplication was the primary mode of replication for IQD genes during evolution. The Ka/Ks ratio indicates that the BjIQD genes underwent strong purifying selection during evolution. GO functional annotation analysis shows that protein binding, tubulin binding, and microtubule binding are the most enriched GO terms. qRT-PCR analysis reveals that the BjIQD genes are regulated in response to Zn stress. Furthermore, some genes lacking the key IQ and DUF4005 domains were analyzed, and we hypothesize that these domain-deficient genes may still perform certain biological functions. This study analyzed the B. juncea IQD gene family from multiple perspectives and explored members lacking key domains. These findings provide insights into the evolution of the BjIQD genes and the analysis of different gene families.

Deciphering the Transition From Tunneling to Band‐Like Transport in Protein‐Templated Biohybrid Junctions

ABSTRACT Protein‐templated metal nanoclusters (MNCs) offer a unique strategy for integrating the structural precision of biological scaffolds with the quantum electronic characteristics of atomically precise metallic cores. Despite this promise, the fundamental principles governing charge transport in such biohybrid systems remain limited. Here, we report a systematic investigation of electron transport in Au/BSA‐MNCs/Au Nanowire junctions incorporating a series of bovine serum albumin (BSA)‐templated metal nanoclusters of copper, silver, and gold (CuNC, AgNC, and AuNC). Incorporation of MNCs yields up to a 17‐fold increase in current relative to native BSA junctions. The conductivity follows the trend AuNC > AgNC > CuNC, a disparity that fragment‐level Density Functional Theory (DFT) analysis attributes to the greater structural robustness and enhanced orbital delocalization of AuNC and AgNC, which together facilitate stronger electronic coupling with proximal protein residues. Temperature‐dependent charge transport measurements (I‐V‐T) further reveal a systematic evolution from tunneling‐dominated to increasingly band‐like transport across the BSA‐MNC series, governed by the extent of electronic delocalization imparted by the metal core. Collectively, these findings provide molecular‐level insight into charge transport in protein‐templated MNCs and establish structure‐property design principles for the next‐generation bioelectronic materials.

Radiomorphometric and texture-based mandibular bone assessment in type 2 diabetes mellitus: correlation with vitamin D, osteocalcin, and glycemic control—an analytical cross-sectional study

Refractive outcomes after cataract surgery using swept-source OCT biometry and image-guided toric IOL alignment: a prospective comparative study in normal versus long axial length eyes

Research on intelligent assembly method of aero-engine deep-cavity nuts based on torque-angle control

Dual Chemical Looping/Catalytic Process for Alkylation of Benzene With Ethane and Propane Yielding Ethylbenzene and Cumene Over Copper‐Containing Mordenite

ABSTRACT Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one‐step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy‐intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper‐containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π‐bounded Cu(I)‐olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi‐functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C–C bond formation and proton transfer step.

Protein trafficking and synaptic demand configure complex and dynamic synaptome architectures of individual neurons

Abstract Excitatory synapses are the most abundant synapse type in the brain. Being essential for behaviour and implicated in hundreds of brain disorders, these synapses exhibit striking structural and functional diversity. Synaptome mapping at single-synapse resolution reveals that synaptic protein diversity is spatially organised along the dendritic tree of individual neurons and varies with age and cell type. However, the cell biological mechanisms underlying the generation of these complex spatial synaptic patterns remain poorly understood. Potential mechanisms include somatic and dendritic protein synthesis, protein trafficking, and local regulatory mechanisms such as activity-dependent degradation. Here we developed computational models to test how combinations of these processes account for empirical synaptome data. We found that a combination of molecular transport mechanisms and local synaptic demand for proteins was sufficient to explain very complex profiles of synaptic protein distributions observed in young, mature and old mice and in different cell types. Our findings suggest the highly complex and dynamic synaptome architecture of the brain is an emergent property of a minimal set of cell biological processes. Our model sets the stage for simulations of brain tissue incorporating molecularly diverse neuronal and synaptic types in a synaptome and connectome architecture.

Correction: Range-wide assessment of habitat suitability for jaguars using multiscale species distribution modelling

From Phenols to Proteins: One‐Pot Biosynthesis and Genetic Encoding of Chalcogen‐Containing Tyrosine Analogues

ABSTRACT Expanding the genetic code with unnatural amino acids (UAAs) offers powerful opportunities to engineer proteins with novel redox and catalytic functions, but is often limited by the need for multistep UAA synthesis and inefficient cellular uptake. Here, we report an integrated biosynthetic–genetic incorporation strategy for chalcogen‐containing proteins from the respective phenols. Structure‐guided engineering of tyrosine phenol lyase (TPL) enabled the enzymatic production of 3‐methoxy‐, 3‐methylthio‐, and 3‐methylseleno‐L‐tyrosine (MeSeY) directly in living cells. Using evolved orthogonal aminoacyl‐tRNA synthetases, these analogues were site‐specifically incorporated into green fluorescent protein (GFP), as confirmed by fluorescence assays, spectroscopy, and mass spectrometry. We further established a one‐pot in vivo system that unifies analogue biosynthesis with translation, reducing precursor requirements and cellular toxicity. This work introduces selenium as a genetically encoded handle for protein engineering and establishes a scalable strategy that couples biocatalysis with genetic code expansion to access redox‐active designer proteins. Importantly, installation of MeSeY at the GFP chromophore residue Tyr66 provides redox‐responsive fluorescence. In a circularly permuted GFP (cpGFP) scaffold, improved chromophore accessibility enables reversible redox switching under H 2 O 2 /thiol cycling.

“Short-term effects of a single kangaroo mother care session on urinary allantoin and maternal–infant bonding in preterm neonates: a quasi-randomized controlled trial”

Abstract Preterm birth is a leading contributor to neonatal morbidity and mortality, often necessitating neonatal intensive care unit (NICU) admission. The resulting separation of mother-infant dyads may escalate physiological stress and impair early bonding. While Kangaroo Mother Care (KMC) is a well-established intervention, evidence regarding the immediate physiological and affective impact of an isolated, short-duration session remains sparse. Thus, this study aimed to evaluate the short-term effects of a single one-hour KMC session on oxidative stress and maternal–infant bonding in preterm neonates. This quasi-randomized controlled trial was conducted at a tertiary care facility in Lahore, Pakistan (February–July 2024). Forty preterm neonate–mother dyads were allocated based on medical record numbers to receive either a single 60 minute KMC session ( n = 20) or standard incubator care ( n = 20). Primary and secondary outcomes included urinary allantoin (measured via ELISA) and Mother–Infant Bonding Scale (MIBS) scores, respectively, assessed at baseline and one hour after the intervention. Data were analysed using paired t-tests and analysis of covariance (ANCOVA). Baseline groups were comparable (p>0.05). Post-intervention, KMC significantly reduced allantoin levels compared to controls (Adjusted Mean Difference [AMD]: −26.18 µmol/mmol; 95% CI: -36.88 to −15.48; p <0.001; partial η 2 =0.399). MIBS scores also improved significantly in the KMC group (AMD: −13.99; 95% CI: −14.84 to −13.14; p <0.001; partial η 2 =0.967). A single one-hour session of Kangaroo Mother Care is associated with reduction in oxidative stress biomarkers and a significant short-term improvement in maternal–infant bonding. These findings suggest that even brief sessions of skin-to-skin contact may serve as potentially effective acute physiological and psychological stabilizer in the NICU setting. However, these immediate effects should be viewed as acute triggers rather than definitive markers of long-term clinical or developmental outcomes. Trial registration : ClinicalTrials.gov, NCT 06338410. Registered 29 March 2024, https://clinicaltrials.gov/study/NCT06338410 .

Visualising backward information propagation in deep reinforcement learning from a variational data assimilation perspective

A multi-task deep learning and radiomics framework for fetal anatomical structure detection and classification in ultrasound imaging

Phosphorus‐Induced Charge Redistribution and Lattice Self‐Regulation in Cu ₃ PSe ₄ Enables Low <i>N</i> / <i>P</i> Ratio and Durable Zn–I ₂ Batteries

ABSTRACT Zn–I 2 batteries is a promising large‐scale energy storage technology, yet conventional Zn metal anode faces challenges including corrosion, dendrite growth, and side reactions, hindering its practical application. Zn 2+ host anodes, leveraging the rocking‐chair mechanism and inherent polyiodide inertness, offer a potential solution to these issues. However, existing host anodes suffer from sluggish Zn 2+ kinetics and low capacity, limiting their compatibility with cathodes. Herein, we report a unique charge and lattice self‐regulation mechanism in Cu 3 PSe 4 that drives expedited Zn 2+ transport and high‐capacity performance. In this configuration, Cu 3 PSe 4 in situ decomposes to P and Cu 2 Se during initial cycling and Cu 2 Se provide subsequent capacity. Importantly, phosphorus modulates the Cu 2 Se lattice, inducing a transition from conventional contraction to expansion during Zn 2+ insertion, thereby enhancing ion transport kinetics and capacity simultaneously. Theoretical calculations reveal that P reconfigures the charge distribution and spatial configuration in Cu 2 Se, reducing Zn 2+ diffusion barrier. Consequently, the optimized Cu 3 PSe 4 anode delivers 150.5 mAh g −1 at 20 A g −1 , and the assembled Cu 3 PSe 4 ||I 2 cell achieves an exceptional lifespan of 30,000 cycles at 9 mg cm −2 with a low N/P ratio of 1.1, demonstrating superior stability. This work provides a novel system of corrosion‐resistant anode for high‐performance and metal‐zinc‐free zinc–iodine batteries.

Retraction Note: Comparing ANI-2x, ANI-1ccx neural networks, force field, and DFT methods for predicting conformational potential energy of organic molecules

Molecular Electrocatalyst Enables Direct Electrochemical Capture and Conversion of CO ₂ up to Atmospheric Concentration

ABSTRACT The conversion of low‐concentration CO 2 streams into fuel is highly desirable for industrial applications, avoiding energy‐intensive CO 2 capture and concentration. Here, we report a highly active molecular electrocatalyst, fac ‐[Mn(CO) 3 (bis‐MeNHC)(MeCN)] + ( 1‐MeCN + ), which enables the direct electrochemical reduction of near‐atmospheric CO 2 concentrations to CO with up to 100% Faradaic efficiency. Voltammetric analysis at varying CO 2 concentrations reveals a clear transition between distinct kinetic regimes, shifting from pure kinetic control to a regime dominated by CO 2 depletion. Kinetic analysis in the 5%–100% CO 2 range reveals a first‐order dependence on substrate concentration. Infrared spectroelectrochemistry confirms that the electrogenerated anionic catalyst remains active under extremely diluted CO 2 conditions. Computational modeling further supports that the CO 2 ‐to‐CO conversion mediated by the doubly reduced species is kinetically accessible at atmospheric CO 2 levels. This work demonstrates molecular electrocatalysis even at CO 2 concentrations as low as 420 ppm (i.e. atmospheric CO 2 partial pressure).

iGraphCTC: an inter-connected graph convolutional network for comprehensive clinical trial collaborations

Abstract Pharmaceutical companies are increasingly expanding their global presence by engaging in collaborative clinical research to meet the growing demand for effective chronic disease treatments. However, identifying suitable affiliations and collaboration networks remains a significant challenge. To tackle this, we propose iGraphCTC, a novel framework for clinical trial collaboration that utilizes an adapted Graph Convolutional Network (GCN) to streamline the identification of potential collaborators. The key contribution lies in its ability to integrate multidimensional clinical data (geographical and intervention attributes) into the recommendation process. Based on both geographical and intervention datasets, iGraphCTC achieves maximum improvements of 16.08% (AUC), 14.28% (F1-Score), and 6.68-17.44% (Accuracy@K). These results highlight its capability to enhance recommendation accuracy by addressing limitations of previous models and integrating clinical insights into the recommendation process. Our results demonstrate the effectiveness of graph-oriented approaches in identifying collaborative activities and pinpointing potential collaborators, providing valuable insights into the dynamics of the pharmaceutical industry’s collaborative landscape.