Local CO Generator Enabled by a CO-Producing Core for Kinetically Enhancing Electrochemical CO2 Reduction to Multicarbon Products.

CO plays a crucial role as an intermediate in electrochemical CO2 conversion to generate multicarbon (C2+) products. However, optimizing the coverage of the CO intermediate (*CO) to improve the selectivity of C2+ products remains a great challenge. Here, we designed a hierarchically structured double hollow spherical nanoreactor featuring atomically dispersed nickel (Ni) atoms as the core and copper (Cu) nanoparticles as the shell, which can greatly improve the catalytic activity and selectivity for C2+ compounds. Within this configuration, CO generated at the active Ni sites on the inner layer accumulates in the cavity before spilling over neighboring Cu sites on the outer layer, thus enhancing CO dimerization within the cavity. Notably, this setup achieves a sustained faradaic efficiency of 74.4% for C2+ production, with partial current densities reaching 337.4 mA cm-2. In situ Raman spectroscopy and finite-element method (FEM) simulations demonstrate that the designed local CO generator can effectively increase the local CO concentration and restrict CO evolution, ultimately boosting C-C coupling. The hierarchically ordered architectural design represents a promising solution for achieving highly selective C2+ compound production in the electroreduction of CO2.

Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

Lysophosphatidic acid responsive photosensitive supramolecular organic frameworks for tumor imaging, drug loading, and photodynamic therapy.

Supramolecular organic frameworks have been widely applied for biological detection and drug delivery. In this study, a supramolecular organic framework (SOF) is constructed through the self-assembly of a highly photosensitive triarylphosphine oxide guest molecule, OTPP-6-Methyl, with cucurbit [8] uril (CB [8]). The formation of the SOF gradually enhances the weak fluorescence of OTPP-6-Methyl owing to the restriction of the molecular folding motion. Although the high positive charge of OTPP-6-Methyl facilitates binding to various negatively charged substances, the SOF system only demonstrated an obvious fluorescence response to LPA, a biomarker of ovarian cancer, via the disassembly of SOF and subsequent binding of OTPP-6-Methyl with LPA. The fluorescence changes during the entire process are insufficient to allow the sensitive detection of LPA; thus, we further designed a FRET system by introducing Cy5, which can act as an energy receptor to achieve a ratiometric readout for LPA. The tumor-targeting cRGD group was introduced into the SOF system as part of another guest molecule, OTPP-5-M-1-cRGD, to improve the tumor-targeting ability of the SOF system. The SOF system further improves the photosensitivity of guest molecules, and is therefore used in the in vivo imaging of ovarian cancer subcutaneous tumors and as a DDS for loading DOX for the combined in vivo chemotherapy and photodynamic treatment of tumors.

Rice Seed Protrusion Quantitative Trait Loci Mapping through Genome-Wide Association Study.

The germination of seeds is a prerequisite for crop production. Protrusion is important for seed germination, and visible radicle protrusion through seed covering layers is the second phase of the process of seed germination. Analyzing the mechanism of protrusion is important for the cultivation of rice varieties. In this study, 302 microcore germplasm populations were used for the GWAS of the protrusion percentage (PP). The frequency distribution of the PP at 48 h and 72 h is continuous, and six PP-associated QTLs were identified, but only qPP2 was detected repeatedly two times. The candidate gene analysis showed that LOC_Os02g57530 (ETR3), LOC_Os01g57610 (GH3.1) and LOC_Os04g0425 (CTB2) were the candidate genes for qPP2, qPP1 and qPP4, respectively. The haplotype (Hap) analysis revealed that Hap1 of ETR3, Hap1 and 3 of GH3.1 and Hap2 and 5 of CTB2 are elite alleles for the PP. Further validation of the germination phenotype of these candidate genes showed that Hap1 of ETR3 is a favorable allele for the germination percentage; Hap3 of GH3.1 is an elite allele for seed germination; and Hap5 of CTB2 is an elite allele for the PP, the germination percentage and the vigor index. The results of this study identified three putative candidate genes that provide valuable information for understanding the genetic control of seed protrusion in rice.

Development and Validation of Potential Molecular Subtypes and Signatures of Thyroid Carcinoma Based on Aging-related Gene Analysis.

BACKGROUND/AIM: Thyroid carcinoma (THCA) is a cancer of the endocrine system that most commonly affects women. Aging-associated genes play a critical role in various cancers. Therefore, we aimed to gain insight into the molecular subtypes of thyroid cancer and whether senescence-related genes can predict the overall prognosis of THCA patients. MATERIALS AND METHODS: Thyroid carcinoma (THCA) transcriptome-related expression profiles were obtained from The Cancer Genome Atlas (TCGA) database. These profiles were randomly divided into training and validation subsets at a ratio of 1:1. Unsupervised clustering algorithms were used to compare differences between the two subtypes; prognosis-related senescence genes were used to further construct our prognostic models by univariate and multivariate Cox analyses and construct a nomogram to predict the 1-, 3-, and 5-year overall survival probability of THCA patients. In addition, we performed gene set enrichment analysis (GSEA) to predict the immune microenvironment and somatic mutations between the different risk groups. Finally, real-time PCR was used to verify the expression levels of key model genes. RESULTS: The 'ConsensusClusterPlus' R package was used to cluster thyroid cancer into two categories (Cluster1 and Cluster2) on the basis of 46 differentially expressed aging-related genes (DE-ARGs); patients in Cluster1 demonstrated a better prognosis than those in Cluster2. Cox analysis was used to screen six prognosis-related DE-ARGs. Finally, our real-time PCR results confirmed our hypothesis. CONCLUSION: Differences exist between the two subtypes of thyroid cancer that help guide treatment decisions. The six DE-ARG genes have a high predictive value for risk stratifying THCA patients.

Precise arrangement of metal atoms at the interface by a thermal printing strategy.

The kinetics and pathway of most catalyzed reactions depend on the existence of interface, which makes the precise construction of highly active single-atom sites at the reaction interface a desirable goal. Herein, we propose a thermal printing strategy that not only arranges metal atoms at the silica and carbon layer interface but also stabilizes them by strong coordination. Just like the typesetting of Chinese characters on paper, this method relies on the controlled migration of movable nanoparticles between two contact substrates and the simultaneous emission of atoms from the nanoparticle surface at high temperatures. Observed by in situ transmission electron microscopy, a single Fe3O4 nanoparticle migrates from the core of a SiO2 sphere to the surface like a droplet at high temperatures, moves along the interface of SiO2 and the coated carbon layer, and releases metal atoms until it disappears completely. These detached atoms are then in situ trapped by nitrogen and sulfur defects in the carbon layer to generate Fe single-atom sites, exhibiting excellent activity for oxygen reduction reaction. Also, sites' densities can be regulated by controlling the size of Fe3O4 nanoparticle between the two surfaces. More importantly, this strategy is applicable to synthesize Mn, Co, Pt, Pd, Au single-atom sites, which provide a general route to arrange single-atom sites at the interface of different supports for various applications.

Synergistic Roles of the CoO/Co Heterostructure and Pt Single Atoms for High-Efficiency Electrocatalytic Hydrogenation of Lignin-Derived Bio-Oils.

Electrochemical hydrogeneration (ECH) of biomass-derived platform molecules, which avoids the disadvantages in utilizing fossil fuel and gaseous hydrogen, is a promising route toward value-added chemicals production. Herein, we reported a CoO/Co heterostructure-supported Pt single atoms electrocatalyst (Pt1-CoO/Co) that exhibited an outstanding performance with a high conversion (>99%), a high Faradaic efficiency (87.6%), and robust stability (24 recyclability) at -20 mA/cm2 for electrochemical phenol hydrogenation to high-valued KA oil (a mixture of cyclohexanol and cyclohexanone). Experimental results and the density functional theory calculations demonstrated that Pt1-CoO/Co presented strong adsorption of phenol and hydrogen on the catalyst surface simultaneously, which was conducive to the transfer of the adsorbed hydrogen generated on the single atom Pt sites to activated phenol, and then, ECH of phenol with high performance was achieved instead of the direct hydrogen evolution reaction. This work described that the multicomponent synergistic single atom catalysts could effectively accelerate the ECH of phenol, which could help the achievement of large-scale biomass upgrading.

Cell-inspired design of cascade catalysis system by 3D spatially separated active sites.

Cells possess isolated compartments that spatially confine different enzymes, enabling high-efficiency enzymatic cascade reactions. Herein, we report a cell-inspired design of biomimetic cascade catalysis system by immobilizing Fe single atoms and Au nanoparticles on the inner and outer layers of three-dimensional nanocapsules, respectively. The different metal sites catalyze independently and work synergistically to enable engineered and cascade glucose detection. The biomimetic catalysis system demonstrates ~ 9.8- and 2-fold cascade activity enhancement than conventional mixing and coplanar construction systems, respectively. Furthermore, the biomimetic catalysis system is successfully demonstrated for the colorimetric glucose detection with high catalytic activity and selectivity. Also, the proposed gel-based sensor is integrated with smartphone to enable real-time and visual determination of glucose. More importantly, the gel-based sensor exhibits a high correlation with a commercial glucometer in real samples detection. These findings provide a strategy to design an efficient biomimetic catalysis system for applications in bioassays and nanobiomedicines.

Active Micelle Pumping Channel Triggers Nonequilibrium Surface Excess Aggregation.

Adsorbate transport during the electrochemical process mostly follows the electric-field direction or the high-to-low direction along the concentration gradient and thus often limits the reactant concentration at the adsorption site and requires specific mechanical or chemical bonds of adsorbates to trigger local excess aggregation for advanced framework structure assembly. Herein, we have discovered an active pumping channel during electrochemical adsorption of a manganese colloid, which follows a low-to-high direction inverse concentration gradient. It triggers surface excess micelle aggregation with even over 16-folds higher concentration than that in bulk owing to hydrogen-bonding difference of the micelle surface between in bulk and at the water surface. Micelles in the channel exhibit unique polymerization behaviors by directly polymerizing monomer micelles to form highly catalytic MnO2 of dendritic frameworks, which can serve as a scalable thin-layer aqueous-phase reactor. It increases the understanding of the interface-dependent dynamic nature of micelle or more adsorbates and inspires transformative synthesizing approaches for advanced oxide materials.

Coupling Single-Atom Sites and Ordered Intermetallic PtM Nanoparticles for Efficient Catalysis in Fuel Cells.

The design of an efficient catalytic system with low Pt loading and excellent stability for the acidic oxygen reduction reaction is still a challenge for the extensive application of proton-exchange membrane fuel cells. Here, a gas-phase ordered alloying strategy is proposed to construct an effective synergistic catalytic system that blends PtM intermetallic compounds (PtM IMC, M = Fe, Cu, and Ni) and dense isolated transition metal sites (M-N4 ) on nitrogen-doped carbon (NC). This strategy enables Pt nanoparticles and defects on the NC support to timely trap flowing metal salt without partial aggregation, which is attributed to the good diffusivity of gaseous transition metal salts with low boiling points. In particular, the resulting Pt1 Fe1 IMC cooperating with Fe-N4 sites achieves cooperative oxygen reduction with a half-wave potential up to 0.94 V and leads to a high mass activity of 0.51 A  mgPt -1 and only 23.5% decay after 30 k cycles, both of which exceed DOE 2025 targets. This strategy provides a method for reducing Pt loading in fuel cells by integrating Pt-based intermetallics and single transition metal sites to produce an efficient synergistic catalytic system.

Axial Dual Atomic Sites Confined by Layer Stacking for Electroreduction of CO2 to Tunable Syngas.

Arranging atoms in an orderly manner at the atomic scale to create stable polyatomic structures is a very challenging task. In this study, we have developed three-dimensional confinement areas on the two-dimensional surface by creating regional defects. These areas are composed of vertically stacked graphene layers, where Ni and Fe atoms are anchored concentrically to form axial dual atomic sites in high yield. These sites can be used to produce tunable syngas through the electroreduction of CO2. Theoretical calculations indicate that the Ni sites vertically regulate the charge distribution of the adjacent Fe sites in the layer below, resulting in a lower d-band center. This, in turn, weakens the adsorption of the *CO intermediate and inhibits the production of H2 at the Fe site. Our research presents a novel approach for concentrated creation of dual atomic sites by building a confinement-selective surface.

The added value of AI-based computer-aided diagnosis in classification of cancer at prostate MRI.

OBJECTIVES: To develop an artificial intelligence (AI) model for prostate segmentation and prostate cancer (PCa) detection, and explore the added value of AI-based computer-aided diagnosis (CAD) compared to conventional PI-RADS assessment. METHODS: A retrospective study was performed on multi-centers and included patients who underwent prostate biopsies and multiparametric MRI. A convolutional-neural-network-based AI model was trained and validated; the reliability of different CAD methods (concurrent read and AI-first read) were tested in an internal/external cohort. The diagnostic performance, consistency and efficiency of radiologists and AI-based CAD were compared. RESULTS: The training/validation/internal test sets included 650 (400/100/150) cases from one center; the external test included 100 cases (25/25/50) from three centers. For diagnosis accuracy, AI-based CAD methods showed no significant differences and were equivalent to the radiologists in the internal test (127/150 vs. 130/150 vs. 125/150 for reader 1; 127/150 vs.132/150 vs. 131/150 for reader 2; all p > 0.05), whereas in the external test, concurrent-read methods were superior/equal to AI-first read (87/100 vs. 71/100, p < 0.001, for reader 2; 79/100 vs. 69/100, p = 0.076, for reader 1) and better than/equal to radiologists (79/100 vs. 72/100, p = 0.039, for reader 1; 87/100 vs. 86/100, p = 1.000, for reader 2). Moreover, AI-first read/concurrent read improved consistency in both internal test (κ = 1.000, 0.830) and external test (κ = 0.958, 0.713) compared to radiologists (κ = 0.747, 0.600); AI-first read method (8.54 s/7.66 s) was faster than readers (92.72 s/89.54 s) and concurrent-read method (29.15 s/28.92 s), respectively. CONCLUSION: AI-based CAD could improve the consistency and efficiency for accurate diagnosis; the concurrent-read method could enhance the diagnostic capabilities of an inexperienced radiologist in unfamiliar situations. KEY POINTS: • For prostate cancer segmentation, the performance of multi-small Vnet displays optimal compared to small Vnet and Vnet (DSCmsvnet vs. DSCsvnet, p = 0.021; DSCmsvnet vs. DSCvnet, p < 0.001). • For prostate gland segmentation, the mean/median DSCs for fine and coarse segmentation were 0.91/0.91 and 0.88/0.89, respectively. Fine segmentation displays superior performance compared to coarse (DSCcoarse vs. DSCfine, p < 0.001). • For PCa diagnosis, AI-based CAD methods improve consistency in internal (κ = 1.000; 0.830) and external (κ = 0.958; 0.713) tests compared to radiologists (κ = 0.747; 0.600); the AI-first read (8.54 s/7.66 s) was faster than the readers (92.72 s/89.54 s) and the concurrent-read method (29.15 s/28.92 s).

A Double Atomic-Tuned RuBi SAA/Bi@OG Nanostructure with Optimum Charge Redistribution for Efficient Hydrogen Evolution.

Charge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic-tuned RuBi SAA/Bi@OG nanostructure that features RuBi single-atom alloy nanoparticle supported by Bi-O single-site-doped graphene was successfully developed by one-step pyrolysis method. The alloyed Bi single atom and adjacent Bi-O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg-1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen-adsorption free energy in HER process. This double atomic-tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts.

Solid Migration to Assemble a Flower-like Nanozyme with Highly Dense Single Copper Sites for Specific Phenol Oxidation.

Nanozymes with high catalytic stability and sustainability have emerged as powerful competitors to natural enzymes for diverse biocatalytic applications. However, constructing a nanozyme with high specificity is one of their biggest challenges. Herein, we develop a facile solid migration strategy to access a flower-like single copper site nanozyme (Cu SSN) via direct transformation of copper foam activated by 2-methylimidazole. With highly clustered CuN3 sites whose local structure is similar to that of natural polyphenol oxidase, the Cu SSN exhibits excellent activity and specificity to oxidize phenols without peroxidase-like activity. Furthermore, the Cu SSN shows high sensitivity in the colorimetric detection of epinephrine with a low detection limit of 0.10 µg mL-1, exceeding that of most previously reported enzyme-mimicking catalysts. This work not only provides a simple method for the large-scale preparation of high-performance nanozymes but also offers an inspiration for the design of highly specific nanozymes by mimicking the synergy among sites in natural enzymes.

Research progress in global digital mental health services for adolescents / 中国学校卫生

Abstract@#The increasing fragile and vulnerable adolescents mental health determines the increasing demand for psychological health services among teenagers, which indicates the inadequacy of traditional mental health service models. This article summarizes the necessity of digital mental health services for adolescents, and then lists the application examples of digital mental health services across the world, aiming to provide reference for digital mental health services among Chinese adolescents.

Adaptive optics system for a short wavelength mid-IR laser based on a Shack-Hartmann wavefront sensor and analysis of thermal noise impacts.

We present an adaptive optics (AO) system for a 1.94-µm laser source. Our system consists of a home-made Shack-Hartmann wavefront sensor and silver-coated bimorph deformable mirror operating in a closed-loop control scheme. The wavefront sensor used an uncooled vapor phase deposition PbSe focal-plane array for the actual light sensing. An effect of thermal afterimage was found to be reducing the centroid detection precision significantly. The effect was analyzed in detail and finally has been dealt with by updating the background calibration. System stability was increased by reduction of control modes. The system functionality and stability were demonstrated by improved focal spot quality. By replacing some of the used optics, the range of the demonstrated mid-IR AOS could be extended to cover the spectral range of 1-5 µm. To the best of our knowledge, it is the first AO system built specifically for mid-IR laser wavefront correction.

Design of Co-Cu Diatomic Site Catalysts for High-efficiency Synergistic CO2 Electroreduction at Industrial-level Current Density.

Single atom catalysts (SACs) have been widely studied in the field of CO2 electroreduction, but industrial-level current density and near-unity product selectivity are still difficult to achieve. Herein, a diatomic site catalysts (DASCs) consisting of Co-Cu hetero-diatomic pairs is synthesized. The CoCu DASC exhibits excellent selectivity with the maximum CO Faradaic efficiency of 99.1 %. The CO selectivity can maintain above 95 % over a wide current density range from 100 mA cm-2 to 500 mA cm-2 . The maximum CO partial current density can reach to 483 mA cm-2 in flow cell, far exceed industrial-level current density requirements (>200 mA cm-2 ). Theoretical calculation reveals that the synergistic catalysis of the Co-Cu bimetallic sites reduce the activation energy and promote the formation of intermediate *COOH. This work shows that the introduction of another metal atom into SACs can significantly affect the electronic structure and then enhance the catalytic activity of SACs.

Precise Regulation of Iron Spin States in Single FeN4 Sites for Efficient Peroxidase-Mimicking Catalysis.

The catalytic activity and selectivity of single-atom sites catalysts is strongly dependent on the supports structure and central metal coordination environment. However, the further optimization of electronic configuration to improve the catalytic performance is usually hampered by the strong coordination effect between the support and metal atoms. Herein, it is discovered that enzyme-mimicking catalytic performance can be enhanced at the fixed coordination single-atom Fe sites by regulating the Fe spin states. The X-ray absorption fine structure, 57 Fe Mössbauer spectrum, and temperature-dependent magnetization measurements reveal that the spin states of Fe in single FeN4  sites can be well manipulated via changing the pyrolysis temperature. The intermediate-spin Fe sites catalyst (t2g 4 eg 1) demonstrates a much higher peroxidase-mimicking activity in comparison with high-spin structure (t2g 3 eg 2). More importantly, the based enzymes system realizes sensitive detection of H2 O2  and glucose by colorimetric sensors with high catalytic activity and selectivity. Furthermore, theoretical calculations unveil that the intermediate-spin FeN4  promotes the OH* desorption process, thus greatly reducing the reaction energy barrier. These findings provide a route to design highly active enzyme-mimicking catalysts and an engineering approach for regulating spin states of metal sites to enhance their catalytic performance.

Periodic One-Dimensional Single-Atom Arrays.

The orderly assembly of single atoms into highly periodic aggregates at the nanoscale is an intriguing but challenging process of high-precision atomic manufacturing. Here, we discover that an in-plane film surface shrinkage can induce molecular self-assembly to arrange single atoms with unconventional distribution, contributing them to periodic one-dimensional segregation on carbon stripes (one-dimensional single-atom arrays (SAA)). This originates from the fact that metal phthalocyanine (MPc) molecules gradually aggregate and melt to form a film under a thermal drive and the help of sodium chloride templates, accompanied by surface shrinkage, self-assembly, and deep carbonization. At the nanoscale, these periodic parallel arrays are formed due to MPc molecular interactions by π-π stacking. At the atomic scale, the single atoms are stabilized by the vertical phthalocyanine-derived multilayer graphene. This can significantly modify the electronic structure of the single-atom sites on the outermost graphene (e.g., Fe-based SAA), thus optimizing the adsorption energy of oxygen intermediates and resulting in a superior oxygen reduction reaction (ORR) performance concerning disordered single atoms. Our findings provide a general route for orderly single-atom manufacturing (e.g., Fe, Co, and Cu) and an understanding of the relationship between orderly allocation and catalytic performance.