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Palladium‐Doping‐Enabled Interface Synergy for Superb Ampere Level Ammonia Electrosynthesis From Nitrate
ABSTRACT The practical electrocatalytic nitrate‐to‐ammonia conversion suffers from insufficient performance at industrial current densities. Here, we report an electrochemically reconstructed Pd‐doped Co catalyst that achieves > 98.0% ammonia Faradaic efficiency at an ultrahigh partial current density of ‒1.43 A cm −2 and operates stably for over 170 h. Integrated in situ spectroscopy and theoretical simulations reveal a dual‐enhancement mechanism, in which Pd doping lowers the energy barrier of the rate‐determining *NO hydrogenation step and reconstructs the interfacial microenvironment. This restructuring promotes cation enrichment and establishes a dynamic hydrogen‐down‐oriented water network, facilitating proton transfer and intermediate stabilization under high‐flux conditions. Unlike its role in Cu‐based systems, Pd in the Co matrix distinctly optimizes the kinetics of surface intermediates, enhances the local interfacial electric field, and increases the flexibility of the hydrogen‐bond network. This work demonstrates the critical synergy between atomic‐site engineering and microenvironment control for achieving high‐rate electrocatalysis beyond conventional electronic modulation.
Frequency of postoperative delirium and associated factors among consultation-liaison psychiatry patients with schizophrenia spectrum disorders undergoing surgery: a retrospective cohort study
DuoFlow-KG: a dual-modal evidence retrieval framework for high-density LLM-augmented KGQA
Palladium‐Catalyzed Three‐Component Coupling Through Carbene Migratory Insertion: Access to Allenes and 1,5‐Enynes
ABSTRACT Palladium‐catalyzed cross‐coupling reactions of propargylic electrophiles with carbon nucleophiles have been established as straightforward and reliable methods for the synthesis of allenes and 1,5‐enynes. However, such transformations have so far been limited to two‐component systems. Herein, we report a palladium‐catalyzed three‐component coupling reaction involving bromoalkynes, diazoesters, and boronates. The reaction proceeds via allenylpalladium or propargylpalladium intermediates, generated through a sequence of oxidative addition, carbene formation, and migratory insertion upon interaction of haloalkynes with diazo compounds under palladium catalysis. Depending on the structure of the boronate substrate, the three‐component coupling selectively delivers either allenes or 1,5‐enynes. DFT calculations provide insight into this substrate‐dependent chemoselectivity. The method exhibits broad substrate scope and has been successfully applied to the concise synthesis of two pharmaceutical agents—aminoglutethimide and anileridine.
Improved deep reinforcement learning controls anti-lock braking via electro-hydraulic composite systems in in-wheel motor-driven electric vehicles
Abstract Anti-lock braking control for in-wheel motor-driven electric vehicles is challenging because electro-hydraulic composite braking combines fast and accurately controllable motor regenerative braking with slower hydraulic pressure regulation. Existing ABS strategies often disable regenerative braking during ABS intervention, which limits both braking performance and energy recovery. This paper proposes a delay-aware action-space-grouped Soft Actor-Critic controller, termed SAC-DA-ASG, for coordinated ABS control of the motor regenerative braking system and the hydraulic braking system. The proposed controller addresses two implementation issues. First, an action-space grouping scheme maps coordinated solenoid-valve operations into a single hydraulic mode, reducing invalid actuator combinations and the policy search space. Second, a delay-aware augmented state incorporates recent system states to compensate for heterogeneous actuator response delays and improve the Markov representation. The controller is trained under randomized road-adhesion and actuator conditions and is evaluated against baseline SAC variants and a Bosch-type ABS strategy. Simulation results show that SAC-DA-ASG keeps the wheel slip ratio closer to the target value of 0.15, reduces slip fluctuation and peak slip, and shortens braking distance under uniform and split- $$\mu$$ road conditions. Sensitivity tests under solenoid-valve delay and vehicle-mass perturbations further indicate robust closed-loop behavior. Real-time hardware-in-the-loop tests on a Speedgoat platform show close agreement with simulation in braking time, stopping distance, and slip-ratio regulation. These results demonstrate the feasibility of DRL-based coordinated electro-hydraulic ABS control for in-wheel motor-driven electric vehicles.
Palladium‐Catalyzed Carbonylative Alternating Copolymerization of Alkynols and Carbon Monoxide
ABSTRACT Conventional methods for polyester synthesis offer limited control over stereochemistry and exhibit constrained functional group tolerance, restricting access to unsaturated polymer architectures with programmable backbone dynamics and critically precluding the formation of ultra‐high‐molecular‐weight (UHMW) chains required for advanced mechanical performance. Here, we report a palladium‐catalyzed carbonylative alternating copolymerization that directly transforms readily available terminal ynols and carbon monoxide into well‐defined unsaturated polyesters. By strategically extending the ynol chain length, we suppress the entropically favored intramolecular cyclization pathway and instead promote intermolecular, enthalpy‐driven chain growth. Ligand engineering of the Pd/phosphine catalytic system achieves exceptional regioselectivity (>99%) for Markovnikov addition, producing regioregular α,β ‐unsaturated polyesters with UHMW ( M n up to 1,390 kDa) and controlled E / Z olefin ratios (up to 99:1). This alkynol‐based carbonylative polymerization establishes a versatile platform for synthesizing functional UHMW polyesters with tailored topologies, addressing long‐standing challenges in precision polyester synthesis and sustainable polymer design.
High adherence to a Mediterranean diet is associated with a diverse faecal microbiome and reduced systemic inflammation in a cohort of pregnant women
A Scalable, Direct‐to‐Biology Platform for Accelerated Discovery of Cereblon‐Based Molecular Glue Degraders
ABSTRACT Molecular glue degraders (MGDs) offer transformative potential for expanding the druggable proteome; however, their discovery is severely impeded by mechanistic complexities that hinder rational design and synthetic bottlenecks that restrict the scale and diversity of E3 ligase‐centric compound libraries. Here, we introduce a general framework that transforms MGD discovery from a serendipity‐driven endeavor into a systematic, scalable pipeline by integrating modular, in situ library assembly with direct‐to‐biology phenotypic screening. Powered by biocompatible primary amine‐based photoclick chemistry, this platform enables the efficient, purification‐free generation of over 1000 structurally diverse cereblon (CRBN)‐centric molecules within days directly in multi‐well plates, facilitating a seamless transition from chemical synthesis to biological evaluation. Applying this strategy, we rapidly identified novel CRBN‐based MGDs that potently and selectively degrade GSPT1 or CK1α, as well as a multi‐target degrader of GSPT1/2 and stearoyl‐CoA desaturase (SCD). Crucially, our integrated validation highlights targeted CK1α degradation as a promising therapeutic strategy for prostate cancer. By leveraging the abundance and structural diversity of primary amines, this scalable platform expands the accessible chemical space, circumventing the complexities of de novo rational design. Ultimately, this work provides a streamlined engine for harnessing diverse E3 ligases, accelerating the development of next‐generation MGDs to tackle intractable diseases.
Deformable multi-head cross attention-based 3D U-net for context-aware multi-modal cardiac image segmentation with uncertainty-aware maps
An Oxygen Self‐Sufficient Nanozyme Engineered From Metal–Organic Cage for Dual‐Modal Self‐Reporting Theranostics
ABSTRACT The development of intelligent theranostic platforms capable of improving tumor‐hypoxic microenvironment and self‐reporting therapeutic status is crucial for overcoming the limitations of conventional photodynamic therapy (PDT). Herein, we report an oxygen self‐sufficient nanozyme by the functionalization of manganese dioxide (MnO 2 ) nanoflowers with supramolecular metal–organic cage (MOC52‐L) photosensitizers for dual‐modal self‐reporting theranostics. This nanozyme integrates catalase‐mimetic activity for oxygen generation with therapeutic enzyme activities, enabling enhanced type I/II combined PDT. The decomposition of MnO 2 component in tumor microenvironment not only efficiently generates oxygen and activates PDT but also specifically triggers the recovery of fluorescence and T1‐weighted magnetic resonance imaging (MRI) signals. The activation of these signals provides real‐time visualization of tumor accumulation and serves as a direct reporter of successful hypoxia alleviation and therapeutic initiation. Moreover, the pockets of MOC52‐L can be employed to capture low‐water‐soluble lificiguat (YC‐1) as effective inhibitors of HIF‐1α for further anti‐angiogenesis and anti‐metastasis. Both in vitro and in vivo studies demonstrated that this nanozyme can non‐invasively visualize the effective treatment zone via signal turn‐on and achieve excellent anti‐tumor performance with high biosafety. This work establishes a generalizable strategy for designing silenced theranostics agents, enabling a single activatable core to enhance imaging‐guided PDT and trigger turn‐on self‐reporting.
Investigating the risk of non-alcoholic fatty liver disease in young patients with psoriasis versus non-psoriatic inflammatory skin diseases
2‐Azaazulenium Hemicyanine Dyes for NIR‐II Multimodal Imaging and Combined Phototherapy
ABSTRACT Hemicyanine dyes are well‐defined donor–π–acceptor molecules whose photophysical and biological properties can be precisely tuned through rational molecular design. However, efficient emitters operating in the second near‐infrared (NIR‐II) region remain scarce, hindering their broader biomedical applications. Here, we report a strategically engineered series of 2‐azaazulenium hemicyanines that achieve bright NIR‐II emission together with multifunctionality. Among them, SWJT‐OCH 3 integrates intense NIR‐II fluorescence with outstanding photothermal and photodynamic performance, enabling multimodal imaging and combined phototherapy when encapsulated into biocompatible nanoparticles (SWJT NPs). Furthermore, an activatable probe (SWJT‐Probe) derived from this platform allows highly sensitive and selective detection of peroxynitrite (ONOO − ) both in vitro and in vivo. This work establishes 2‐azaazulenium hemicyanines as versatile molecular scaffolds and provides a promising design paradigm for multifunctional NIR‐II fluorophores with broad biomedical potential.
First Eocene lizard (Squamata) from Balkanatolia documents overwater dispersal of Paleogene pleurodontan iguanians
Abstract We here describe a fossil jaw fragment from the middle Eocene (Lutetian) Uzunçarşıdere Formation in Anatolia, pertaining to a pleurodontan iguanian. This region during most of the Eocene was part of an isolated insular landmass, called Balkanatolia, that is mostly known for its peculiar and diverse insular mammalian fauna. The lizard specimen represents the first evidence of Eocene reptiles from Balkanatolia, providing a first glimpse into the herpetofaunas of this, now lost, insular landmass. The fossil material is rather fragmentary, precluding a more precise identification, but its distinctive tooth morphology confirms the presence of pleurodontan iguanians in the region for the first time. The presence of a distinct mesiodistal groove along the apical crest of the central cusp in the teeth of the Anatolian pleurodontan is of particular interest, as this feature is otherwise observed only in the Eocene genera Cadurciguana from Western Europe and Parasauromalus from North America, plus the extant American lineages of Dactyloidae, Leiocephalidae, and Polychrotidae. Interestingly, this feature seems to be absent from all other pleurodontans, including the abundant Eocene corytophanid Geiseltaliellus . The new find indicates another successful overseas dispersal of pleurodontans, a group that has repeatedly colonized distant landmasses, including oceanic islands, throughout its evolutionary history. Taking into consideration the diversity and abundance of pleurodontans in the Eocene of Europe and the total absence of the group from coeval Africa and Asia, it is likely that the new Anatolian iguana arrived from the former continent sometime between the early and early middle Eocene.
Gene panel analysis for oocyte/zygote/embryo maturation arrest in female infertility: a multicenter study in Japan
Abstract Oocyte/zygote/embryo maturation arrest (OZEMA) causes recurrent failure of oocyte maturation, fertilization, or early embryonic development, but its genetic basis and clinically useful testing indicators remain unclear in Japanese patients. We performed a multicenter retrospective cohort study of 50 Japanese women with primary infertility who repeatedly exhibited OZEMA across multiple retrieval cycles. Whole-exome sequencing was used to analyze 24 OZEMA-associated genes, and pathogenic or likely pathogenic variants were classified according to ACMG/AMP guidelines. Pathogenic or likely pathogenic variants were identified in 10 patients (20%), most frequently in TUBB8 ( n = 6), followed by PATL2 , ZP2 , ZP3 , and CHEK1 ( n = 1 each). Variant-positive patients had markedly fewer metaphase II oocytes, fertilized oocytes, day-3 embryos, transfer-eligible day-3 embryos, and blastocysts than variant-negative patients. No variant-positive patient achieved a day-3 embryo. Failure to achieve day-3 embryos showed 100% sensitivity and 82.5% specificity for predicting pathogenic or likely pathogenic variants, with higher specificity than failure to achieve transfer-eligible day-3 embryos or blastocysts. These findings characterized OZEMA-associated genetic variants in a Japanese multicenter cohort and suggest that failure to achieve day-3 embryos may help identify patients who require genetic testing.
Anti‐Heavy‐Atom Effect Boosts Electroluminescence in Copper Cluster‐Based LEDs
ABSTRACT The heavy‐atom effect plays a pivotal role in promoting intersystem crossing and enhancing phosphorescence. However, its impact on electroluminescence in light‐emitting diode (LED) devices remains largely unexplored, and a clear molecular‐level understanding is still lacking. Herein, we report a nearly isostructural pair of copper(I) clusters, [Cu 4 S(dppm) 4 ](PF 6 ) 2 ( Cu 4 S ) and [Cu 4 Se(dppm) 4 ](PF 6 ) 2 ( Cu 4 Se ), which differ solely by a single‐atom substitution of the central S 2− ( Z = 16) with Se 2− ( Z = 34). Despite exhibiting nearly identical photoluminescence (PL) characteristics and comparable external quantum efficiencies (EQEs) in non‐doped devices (5.8% vs. 5.5%), the lighter‐atom‐incorporated Cu 4 S consistently outperforms its heavier analog Cu 4 Se across three distinct host matrices. In particular, the Cu 4 S ‐based device employing the thermally activated delayed fluorescence (TADF) hosts achieved a maximum EQE of 20.9% at λ EL = 608 nm , significantly surpassing that of devices with Cu 4 Se (12.9%). Systematic studies reveal that the S‐centered cluster exhibits stronger resistance to concentration quenching, more enhanced charge transport, and a significantly reduced trap‐state density, thereby effectively circumventing heavy‐atom‐induced non‐radiative losses during electroluminescence. These findings demonstrate that single‐atom variations within the cluster core decisively govern EL efficiency via an anti‐heavy‐atom effect and provide a new strategy for improving LED performance by exploiting this effect.
Author Correction: Peripheral blood CD14 + monocytes in luminal breast carcinoma subtypes: in preliminary research and overview of candidate biomarker proteins
Sub1 contributes to heart failure with preserved ejection fraction driven by aging in mice
Shoupeng Cao
The Importance of Ligand Coverage on Nanocatalysis: Optimizing CO <sub>2</sub> Electroreduction Activity on Pyridine Modified Gold Nanoparticles
ABSTRACT Ligand retention or modification at the surfaces of nanocatalysts can modulate catalytic performance, but the role of ligand coverage is often underappreciated. Herein, we systematically investigate the effect of pyridine ligand coverage on the electrocatalytic CO 2 reduction reaction (CO 2 RR) of gold (Au) nanoparticles. An optimal pyridine coverage (θ = 55%) yields maximal CO 2 RR performance, with a CO Faradaic efficiency of ∼100% and a CO mass activity of 1.11 A mg −1 . Combined physical characterization, in situ electrochemical infrared spectroscopy, and theoretical calculations reveal that increasing pyridine coverage progressively renders the Au surface more negatively charged. The elevated surface electron density alters the interfacial water structure from isolated H 2 O to strongly hydrogen‐bonded networks, facilitating formation of the key *COOH intermediate. Concurrently, the electron‐rich Au surface weakens CO adsorption, promoting CO desorption and thereby enhancing both activity and selectivity toward CO. The optimal pyridine coverage represents a balance between electronic promotion of intermediate formation and steric effects of the ligand, enabling concurrently favorable *COOH generation and CO desorption. These findings establish ligand coverage as a critical parameter for tuning nanocatalyst behavior and suggest that coverage optimization may be broadly applicable across catalytic systems.