Rapid Defect Engineering in FeCoNi/FeAl2O4 Hybrid for Enhanced Oxygen Evolution Catalysis: A Pathway to High-Performance Electrocatalysts.

Rational modulation of surface reconstruction in the oxygen evolution reaction (OER) utilizing defect engineering to form efficient catalytic activity centers is a topical interest in the field of catalysis. The introduction of point defects has been demonstrated to be an effective strategy to regulate the electronic configuration of electrocatalysts, but the influence of more complex planar defects (e.g., twins and stacking faults), on their intrinsic activity is still not fully understood. This study harnesses ultrasonic cavitation for rapid and controlled introduction of different types of defects in FeCoNi/FeAl2O4 hybrid coatings, optimizing OER catalytic activity. Theoretical calculations and experiments demonstrate that the different defects optimize the coordination environment and facilitate the activation of surface reconstruction into true catalytic activity centers at lower potentials. Moreover, it demonstrates exceptional durability, maintaining stable oxygen production at a high current density of 300 mA cm-2 for over 120 hours. This work not only presents a novel pathway for designing advanced electrocatalysts but also deepens our understanding of defect-engineered catalytic mechanisms, showcasing the potential for rapid and efficient enhancement of electrocatalytic performance.

Pallidum volume as a predictor for the effectiveness of mindfulness-based cognitive therapy and psycho-education in unmedicated patients with obsessive-compulsive disorder.

BACKGROUND: Mindfulness-based cognitive therapy (MBCT) has been documented to be effective in treating obsessive-compulsive disorder (OCD). However, the neurobiological basis of MBCT remains largely elusive, which makes it clinically challenging to predict which patients are more likely to respond poorly. Hence, identifying biomarkers for predicting treatment outcomes holds both scientific and clinical values. This prognostic study aims to investigate whether pre-treatment brain morphological metrics can predict the effectiveness of MBCT, compared with psycho-education (PE) as an active placebo, among patients with OCD. METHODS: A total of 32 patients with OCD were included in this prognostic study. They received magnetic resonance imaging (MRI) brain scans before treatment. Subsequently, 16 patients received 10 weeks of MBCT, while the other 16 patients underwent a 10-week PE program. The effectiveness of the treatments was primarily assessed by the reduction rate of the Yale-Brown Obsessive-Compulsive Scale (Y-BOCS) total score before and after the treatment. We investigated whether several predefined OCD-associated brain morphological metrics, selected based on prior published studies by the ENIGMA Consortium, could predict the treatment effectiveness. RESULTS: Both the MBCT and PE groups exhibited substantial reductions in Y-BOCS scores over 10 weeks of treatment, with the MBCT group showing a larger reduction. Notably, the pallidum total volume was associated with treatment effectiveness, irrespective of the intervention group. Specifically, a linear regression model utilizing the pre-treatment pallidum volume to predict the treatment effectiveness suggested that a one-cubic-centimeter increase in pallidum volume corresponded to a 22.3% decrease in the Y-BOCS total score reduction rate. CONCLUSIONS: Pallidum volume may serve as a promising predictor for the effectiveness of MBCT and PE, and perhaps, other treatments with the shared mechanisms by MBCT and PE, among patients with OCD.

Reversing Zincophobic/Hydrophilic Nature of Metal-N-C via Metal-Coordination Interaction for Dendrite-Free Zn Anode with High Depth-of-Discharge.

Dendrite-free Zn metal anodes with high depth-of-discharge (DoD) and robust cycle performances are highly desired for the practical application of aqueous Zn-ion batteries. Herein, the zincophobic/hydrophilic nature of Metal-N-C through manipulating the electronic interactions between metal and coordination atoms is successfully reversed, thereby fabricating a zincophilic/hydrophobic asymmetric Zn-N3Py+1Pr-C (consisting of a Zn center coordinated with 3 pyridinic N atoms and 1 pyrrolic N atom) host, which realizes uniformed Zn deposition and a long lifespan with high DoD. The experimental and theoretical investigations demonstrate weakened interaction between pyrrolic N and metal center in the asymmetric Zn-N3Py+1Pr-C triggers downshift of the Zn 3d-band-center and a new localization nonbonding state in the N and C 2p-band, resulting in preferred Zn adsorption to water adsorption. Consequently, the asymmetric Zn-N3Py+1Pr-C host delivers small Zn nucleation overpotential and high Coulombic efficiency of 98.3% over 500 cycles. The symmetric cells with Zn-N3Py+1Pr-C@Zn anode demonstrate 500 h dendrite-free cycles at DoD up to 50%. The Zn-N3Py+1Pr-C@Zn/S-PANI full cell also shows a robust long-term cycle performance of 1000 cycles at 10 A g-1. This strategy of constructing zincophilic/hydrophobic Metal-N-C may open up their application for the dendrite-free metal anode.

ICP-MS and fluorescence dual-mode detection of ZIKV-RNA based on quantum dot labeling with hybridization chain reaction.

The detection of Zika virus (ZIKV) is of great significance to human life and health. Herein, we presented an ICP-MS and fluorescent dual-mode sensor for quantitative analysis of Zika virus RNA fragments (ZIKV-RNA), which employed quantum dots (QDs) as signal tags and combined with hybridization chain reaction (HCR). The dual-mode sensor realized cross-checking of the analysis results and improved the assay accuracy. Firstly, the single-stranded DNA (ssDNA) was anchored on the surface of magnetic beads (MBs). Afterward, HCR was conducted with probe DNA-CdSe quantum dots conjugates (pDNA-QDs) and link DNA (lDNA), producing the MBs-ssDNA-[pDNA-QDs-lDNA]n conjugates. In the presence of target ZIKV-RNA, a strand displacement reaction occurred, leading to the dissociation of the [pDNA-QDs-lDNA]n labels from the conjugates into the solution. Finally, the signal intensity was detected using ICP-MS and fluorescence analysis, with achieved limits of detection of 131 pM and 152 pM, respectively. The inter-assay RSD values of fluorescence and ICP-MS were 3.94 % and 4.26 % at 10 nM level, respectively, showing that the method had good precision. This method showed high selectivity and was applied to the analysis of biological fluids. There was no significant difference between the results of ICP-MS modes and fluorescence mode. This method offers a new strategy for sensitivity analysis of ZIKV-RNA and exhibits promise in clinical applications for diagnosis.

Janus particles with tunable patch symmetry and their assembly into chiral colloidal clusters.

Janus particles, which have an attractive patch on the otherwise repulsive surface, have been commonly employed for anisotropic colloidal assembly. While current methods of particle synthesis allow for control over the patch size, they are generally limited to producing dome-shaped patches with a high symmetry (C∞). Here, we report on the synthesis of Janus particles with patches of various tunable shapes, having reduced symmetries ranging from C2v to C3v and C4v. The Janus particles are synthesized by partial encapsulation of an octahedral metal-organic framework particle (UiO-66) in a polymer matrix. The extent of encapsulation is precisely regulated by a stepwise, asymmetric dewetting process that exposes selected facets of the UiO-66 particle. With depletion interaction, the Janus particles spontaneously assemble into colloidal clusters reflecting the particles' shapes and patch symmetries. We observe the formation of chiral structures, whereby chirality emerges from achiral building blocks. With the ability to encode symmetry and directional bonding information, our strategy could give access to more complex colloidal superstructures through assembly.

Self-Decoupled Oxygen Electrocatalysis for Ultrastable Rechargeable Zn-Air Batteries with Mild-Acidic Electrolyte.

Rechargeable zinc-air batteries (ZABs) have been considered promising as next-generation sustainable energy storage devices; however, their large-scale deployment is hampered by the unsatisfactory cyclic lifespan. Employing neutral and mild-acidic electrolytes is effective in extending the cyclability, but the rapid performance degradation of the bifunctional catalysts owing to different microenvironmental requirements of the alternative oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is still a serious limitation of their cyclic life. Herein, we propose a "self-decoupling" strategy to significantly improve the stability of the bifunctional catalysts by constructing a smart interface in the bifunctional air electrode. This smart interface, containing a resistance-switchable sulfonic acid doped polyaniline nanoarray interlayer, is nonconductive at high potential but conductive at low potential, which enables spontaneous electrochemical decoupling of the bifunctional catalyst for the ORR and OER, respectively, and thus protects it from degradation. The resulting self-decoupled mild-acidic ZAB delivers stable cyclic performances in terms of a negligible energy efficiency loss of 0.015% cycle-1 and 3 times longer cycle life (∼1400 h) compared with the conventional mild-acidic ZAB using a normal bifunctional air electrode and the same low-cost ZnCo phosphide/nitrogen-doped carbon bifunctional catalyst. This work provides an effective strategy for tolerating alternative oxidation-reduction reactions and emphasizes the importance of smart nanostructure design for more sustainable batteries.

Dynamic-self-catalysis as an accelerated air-cathode for rechargeable near-neutral Zn-air batteries with ultrahigh energy efficiency.

Neutral/near-neutral electrolyte rechargeable zinc-air batteries (NN-ZABs) with long cycling lifetime are an evolutionary design of the conventional alkaline ZABs, but the extremely sluggish kinetics of oxygen electrocatalysis in mild pH solutions in the air-cathode has notably affected the energy efficiency of the NN-ZABs. Herein, we present a dynamic self-catalysis as the air-cathode chemistry to boost the energy efficiency of NN-ZABs, which is based on in situ reversible generation of highly active electrocatalysts from the electrolyte during the discharge and charge operations of ZABs, respectively. Two reversible redox reactions of Cu(I)/Cu(II) and Mn(II)/Mn(IV) in the NH4Cl-ZnCl2-based electrolyte are integrated with oxygen electrocatalysis in the air-cathode to in situ generate Cu(I)-O-Cl deposits during discharging and Cu-MnO2 deposits during charging, which directly catalyze the subsequent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. The in situ generated electrocatalysts deliver good oxygen electrocatalytic activities due to their distinctive surface structures and can be dissolved by potential reversal in a subsequent battery operation. The NN-ZAB designed as such delivers a record-high energy efficiency of 69.0% and a cycling life of 1800 h with an areal capacity of 10 mA h cm-2, surpassing the performances of NN-ZABs with preloaded electrocatalysts reported to date.

Water-Trapping Single-Atom Co-N4 /Graphene Triggering Direct 4e- LiOH Chemistry for Rechargeable Aprotic Li-O2 Batteries.

Lithium-oxygen (Li-O2 ) batteries have received extensive attention owing to ultrahigh theoretical energy density. Compared to typical discharge product Li2 O2 , LiOH has attracted much attention for its better chemical and electrochemical stability. Large-scale applications of Li-O2 batteries with LiOH chemistry are hampered by the serious internal shuttling of the water additives with the desired 4e- electrochemical reactions. Here, a metal organic framework-derived "water-trapping" single-atom-Co-N4 /graphene catalyst (Co-SA-rGO) is provided that successfully mitigates the water shuttling and enables the direct 4e- catalytic reaction of LiOH in the aprotic Li-O2 battery. The Co-N4 center is more active toward proton-coupled electron transfer, benefiting - direction 4e- formation of LiOH. 3D interlinked networks also provide large surface area and mesoporous structures to trap ≈12 wt% H2 O molecules and offer rapid tunnels for O2 diffusion and Li+ transportation. With these unique features, the Co-SA-rGO based Li-O2 battery delivers a high discharge platform of 2.83 V and a large discharge capacity of 12 760.8 mAh g-1 . Also, the battery can withstand corrosion in the air and maintain a stable discharge platform for 220 cycles. This work points out the direction of enhanced electron/proton transfer for the single-atom catalyst design in Li-O2 batteries.

Electron Redistribution Enables Redox-Resistible Li6 PS5 Cl towards High-Performance All-Solid-State Lithium Batteries.

Sulfide electrolytes with high ionic conductivity hold great promise for all-solid-state lithium batteries. However, the parasitic redox reactions between sulfide electrolyte and Li metal result in interfacial instability and rapid decline of the battery performance. Herein, a redox-resistible Li6 PS5 Cl (LPSC) electrolyte is created by regulating the electron distribution in LPSC with Mg and F incorporation. The introduction of Mg triggers the electron agglomeration around S atom, inhibiting the electron acceptance from Li, and F generates the self-limiting interface, which hinders the redox reactions between LPSC and Li metal. This redox-resistible Li6 PS5 Cl-MgF2 electrolyte therefore presents a high critical current density (2.3 times that of pristine electrolyte). The LiCoO2 /Li6 PS5 Cl-MgF2 /Li cell shows an outstanding cycling stability (93.3 %@100 cycles at 0.2 C). This study highlights the electronic structure modulation to address redox issues on sulfide-based lithium batteries.

Brain White Matter Structural Alteration in Hemifacial Spasm: A Diffusion Tensor Imaging Study.

OBJECTIVE: To analyze the changes in the white matter structure of the whole brain in hemifacial spasm (HFS) patients by using the tract-based spatial statistics (TBSS) method. MATERIALS AND METHODS: 29 HFS patients without anxiety and depression and 29 healthy controls with matching age, sex, and education were selected. All subjects received a 3.0T magnetic resonance (MR) brain diffusion tensor imaging scan. Tract-based spatial statistics method was used to analyze the changes in white matter structure in the whole brain and obtained the cerebral white matter fibrous areas exhibiting significant intergroup differences. The fractional anisotropy (FA), mean diffusivity, axial diffusivity, and radial diffusivity of these areas were abstracted. Analyzed the correlation between these diffusion metrics and clinical variables (disease duration, spasm severity). RESULTS: Compared with the healthy controls group, the HFS group exhibited significantly lower FA in the forceps minor, bilateral anterior thalamic radiation, and right superior longitudinal fasciculus ( P <0.05, threshold-free cluster enhancement corrected). Cohen grading scale of HFS patients was negatively correlated with FA of forceps minor. CONCLUSION: Based on TBSS analysis, the injury of white matter fiber tracts in HFS patients was found, including forceps minor, bilateral anterior thalamic radiation, and right superior longitudinal fasciculus. The changes of FA values in forceps minor were negatively correlated with the Cohen grading scale, suggesting that the alteration of white matter fiber in the genu-of-corpus-callosum-cortex circuit plays an important role in the neuro-pathological mechanism of HFS. Combined with previous research, it is also necessary to further explore the change of the superior longitudinal fasciculus in the future.

Constructing a Superlithiophilic 3D Burr-Microsphere Interface on Garnet for High-Rate and Ultra-Stable Solid-State Li Batteries.

Garnet-type solid-state electrolyte (SSE) Li6.5 La3 Zr1.5 Ta0.5 O12 attracts great interest due to its high ion conductivity and wide electrochemical window. But the huge interfacial resistance, Li dendrite growth, and low critical current density (CCD) block the practical applications. Herein, a superlithiophilic 3D burr-microsphere (BM) interface layer composed of ionic conductor LiF-LaF3 is constructed in situ to achieve a high-rate and ultra-stable solid-state lithium metal battery. The 3D-BM interface layer with a large specific surface area shows a superlithiophilicity and its contact angle with molten Li is only 7° enabling the facile infiltration of molten Li. The assembled symmetrical cell reaches one of the highest CCD (2.7 mA cm-2 ) at room temperature, an ultra-low interface impedance of 3 Ω cm2 , and a super-long cycling stability of 12 000 h at 0.1-1.5 mA cm-2 without Li dendrite growth. The solid-state full cells with 3D-BM interface show outstanding cycling stability (LiFePO4 : 85.4%@900 cycles@1 C; LiNi0.8 Co0.1 Mn0.1 O2 :89%@200 cycles@0.5 C) and a high rate capacity (LiFePO4 :135.5mAh g-1 at 2 C). Moreover, the designed 3D-BM interface is quite stable after 90 days of storage in the air. This study offers a facile strategy to address the critical interface issues and accelerate the practical application of garnet-type SSE in high performance solid-state lithium metal batteries.

Constructing Sandwich-Structured Poly(vinyl alcohol) Composite Films with Thermal Conductive and Electrical Performance.

With the miniaturization and high integration development in microelectronic devices, the problem of heat dissipation has attracted widespread attention. Highly thermal conductive and electrical insulation polymer composites show great advantages to solve the problems of heat dissipation. Nevertheless, the fabrication of polymer composites with both excellent thermal conductivity and electrical performance is still a great challenge. Herein, to coordinate the thermal and electrical properties of the composite film, the sandwich-structured poly(vinyl alcohol) (PVA)/boron phosphide (BP)-boron nitride nanosheet (BNNS) composite films were prepared, with the PVA/BP composite film as the top and bottom layers and the BNNS layer as the middle layer. When the filler loading was 31.92 wt %, the sandwich-structured composite films showed excellent in-plane thermal conductivity (9.45 W·m-1·K-1), low dielectric constant (1.25 at 102 Hz), and excellent breakdown strength. In the composite film, the interconnected BP particles and BNNS layer formed several heat dissipation pathways to increase the thermal conductivity, while the insulated BNNS layer hampered the electron transformation to enhance the electrical resistivity of films. Therefore, the PVA/BP-BNNS composite films showed a potential application in heat dissipation of high power electronic devices.

Multicytokine-producing CD4+ T cells characterize the livers of patients with NASH.

A role of CD4+ T cells during the progression from nonalcoholic fatty liver disease (NAFLD) to nonalcoholic steatohepatitis (NASH) has been suggested, but which polarization state of these cells characterizes this progression and the development of fibrosis remain unclear. In addition, a gut-liver axis has been suggested to play a role in NASH, but the role of CD4+ T cells in this axis has just begun to be investigated. Combining single-cell RNA sequencing and multiple-parameter flow cytometry, we provide the first cell atlas to our knowledge focused on liver-infiltrating CD4+ T cells in patients with NAFLD and NASH, showing that NASH is characterized by a population of multicytokine-producing CD4+ T cells. Among these cells, only those with a Th17 polarization state were enriched in patients with advanced fibrosis. In parallel, we observed that Bacteroides appeared to be enriched in the intestine of NASH patients and to correlate with the frequency of multicytokine-producing CD4+ T cells. In short, we deliver a CD4+ T cell atlas of NAFLD and NASH, providing the rationale to target CD4+ T cells with a Th17 polarization state to block fibrosis development. Finally, our data offer an early indication to test whether multicytokine-producing CD4+ T cells are part of the gut-liver axis characterizing NASH.

Single-cell transcriptomics reveals a mechanosensitive injury signaling pathway in early diabetic nephropathy.

BACKGROUND: Diabetic nephropathy (DN) is the leading cause of end-stage renal disease, and histopathologic glomerular lesions are among the earliest structural alterations of DN. However, the signaling pathways that initiate these glomerular alterations are incompletely understood. METHODS: To delineate the cellular and molecular basis for DN initiation, we performed single-cell and bulk RNA sequencing of renal cells from type 2 diabetes mice (BTBR ob/ob) at the early stage of DN. RESULTS: Analysis of differentially expressed genes revealed glucose-independent responses in glomerular cell types. The gene regulatory network upstream of glomerular cell programs suggested the activation of mechanosensitive transcriptional pathway MRTF-SRF predominantly taking place in mesangial cells. Importantly, activation of MRTF-SRF transcriptional pathway was also identified in DN glomeruli in independent patient cohort datasets. Furthermore, ex vivo kidney perfusion suggested that the regulation of MRTF-SRF is a common mechanism in response to glomerular hyperfiltration. CONCLUSIONS: Overall, our study presents a comprehensive single-cell transcriptomic landscape of early DN, highlighting mechanosensitive signaling pathways as novel targets of diabetic glomerulopathy.

AdaDiag: Adversarial Domain Adaptation of Diagnostic Prediction with Clinical Event Sequences.

Early detection of heart failure (HF) can provide patients with the opportunity for more timely intervention and better disease management, as well as efficient use of healthcare resources. Recent machine learning (ML) methods have shown promising performance on diagnostic prediction using temporal sequences from electronic health records (EHRs). In practice, however, these models may not generalize to other populations due to dataset shift. Shifts in datasets can be attributed to a range of factors such as variations in demographics, data management methods, and healthcare delivery patterns. In this paper, we use unsupervised adversarial domain adaptation methods to adaptively reduce the impact of dataset shift on cross-institutional transfer performance. The proposed framework is validated on a next-visit HF onset prediction task using a BERT-style Transformer-based language model pre-trained with a masked language modeling (MLM) task. Our model empirically demonstrates superior prediction performance relative to non-adversarial baselines in both transfer directions on two different clinical event sequence data sources.

Low-dimensional assemblies of metal-organic framework particles and mutually coordinated anisotropy.

Assembling metal-organic framework (MOF)-based particles is an emerging approach for creating colloidal superstructures and hierarchical functional materials. However, realization of this goal requires strategies that not only regulate particle interactions but also harness the anisotropic morphologies and functions of various frameworks. Here, by exploiting depletion interaction induced by ionic amphiphiles, we show the assembly of a broad range of low-dimensional MOF colloidal superstructures, including 1D straight chains, alternating or bundled chains, 2D films of hexagonal, square, centered rectangular, and snowflake-like architectures, and quasi-3D supercrystals. With well-defined polyhedral shapes, the MOF particles are mutually oriented upon assembly, producing super-frameworks with hierarchically coordinated crystallinity and micropores. We demonstrate this advantage by creating functional MOF films with optical anisotropy, in our cases, birefringence and anisotropic fluorescence. Given the variety of MOFs available, our technique should allow access to advanced materials for sensing, optics, and photonics.

Investigation into the Properties of L-5-Methyltetrahydrofolate and Seal Oil as a Potential Atherosclerosis Intervention in Rats.

Atherosclerosis is a chronic inflammatory disease that leads to tissue ischemia. As the biologically active form of folic acid, L-5-methyltetrahydrofolate (L-5-MTHF) can improve endothelial function. And Seal oil plays a beneficial role in the progression of atherosclerosis. The study aims to evaluate beneficial effects of L-5-MTHF alone or in combination with Seal oil on atherosclerosis. Seventy-two male Wistar rats were randomly divided into 6 groups: control (normal diet), atherosclerosis (high-fat diet), folic acid (high-fat+3 mg/kg folic acid), low-dose L-5-MTHF (high-fat+3 mg/kg L-5-MTHF), low-dose L-5-MTHF+Seal oil (high-fat+3 mg/kg L-5-MTHF+0.5 g/kg Seal oil), high-dose L-5-MTHF (high-fat+10 mg/kg L-5-MTHF). After 13 wk, rats were sacrificed. Rats exhibiting atherosclerosis had dyslipidemia and serious aortic lesions. Supplementation with low-dose L-5-MTHF+Seal oil or use of high-dose L-5-MTHF increased serum folate concentrations, decreased homocysteine levels, improved the serum lipid profile, up-regulated expression of NO and NOS, enhancement of the antioxidant properties of GSH-Px activity and reduction in the concentration of MDA, levels of Olr1 and RelA mRNA decreased in aortic tissues, and expression of inflammatory factors, TNF-α, IL-6, IL-1ß and endothelial cell injury factors ET-1 and sICAM-1, were also down-regulated. In addition, HD-L-5-MTHF increased the antioxidant activity of serum SOD. We conclude that L-5-MTHF has obvious anti-inflammatory and antioxidant effects on diseased blood vessels. The intervention of L-5-MTHF alone or in combination with Seal oil can improve atherosclerosis in rats and reduce the occurrence of aortic lesions. The anti-atherosclerotic mechanism may be related to down-regulation of Olr1 and RelA expression.

Deletion of Smooth Muscle Lethal Giant Larvae 1 Promotes Neointimal Hyperplasia in Mice.

Vascular smooth muscle cell (VSMC) proliferation and migration contribute to neointimal hyperplasia after injury, which causes vascular remodeling related to arteriosclerosis, hypertension, and restenosis. Lethal giant larvae 1 (LGL1) is a highly conserved protein and plays an important role in cell polarity and tumor suppression. However, whether LGL1 affects neointimal hyperplasia is still unknown. In this study, we used smooth muscle-specific LGL1 knockout (LGL1SMKO) mice generated by cross-breeding LGL1flox/flox mice with α-SMA-Cre mice. LGL1 expression was significantly decreased during both carotid artery ligation in vivo and PDGF-BB stimulation in vitro. LGL1 overexpression inhibited the proliferation and migration of VSMCs. Mechanistically, LGL1 could bind with signal transducer and activator of transcription 3 (STAT3) and promote its degradation via the proteasomal pathway. In the carotid artery ligation animal model, smooth muscle-specific deletion of LGL1 accelerated neointimal hyperplasia, which was attenuated by the STAT3 inhibitor SH-4-54. In conclusion, LGL1 may inhibit neointimal hyperplasia by repressing VSMC proliferation and migration via promoting STAT3 proteasomal degradation.