Macrophage exosomes mediate palmitic acid-induced metainflammation by transferring miR-3064-5p to target IκBα and activate NF-κB signaling.

INTRODUCTION: High palmitic acid (PA) levels trigger metainflammation, facilitating the onset and progression of chronic metabolic diseases. Recently, exosomes were identified as new inflammation mediators. However, the mechanism by which macrophage exosomes mediate PA-induced inflammation remains unclear. OBJECTIVES: To explore how PA induces metainflammation through macrophage exosomes. METHODS: Exosomes secreted by RAW264.7 mouse macrophages stimulated with PA (ExosPA) or not (Exos) were prepared by ultracentrifugation. The differential miRNAs between ExosPA and Exos were identified by high-throughput sequencing, and their targeted mRNAs and proteins were bioinformatically analyzed and verified by qPCR and western blot. Mouse macrophages and metabolic cells (AML-12 hepatocytes, C2C12 myocytes or 3T3-L1 adipocytes) were treated with ExosPA or Exos. The verified miRNAs and its targeted molecules related to inflammation were analyzed in recipient cells. Furthers, exosomes were prepared from primary peritoneal macrophages isolated from AIN93G diet-fed (Control PM-Exos) or HPD-fed (PA PM-Exos) mice. Control or PA PM-Exos were then tail vein injected (30 µg) into mice (n = 10), once a week for 2 weeks. The verified miRNA and its targets in blood, blood exosomes, and metabolic tissues were detected. Finally, measured the levels of miRNA, inflammatory factors, and fatty acids in the blood of 20 obese/overweight individuals and 20 healthy individuals. RESULTS: ExoPA activate NF-κB signaling and enhance inflammatory enzyme/cytokine production in macrophages and metabolic cells. ExoPA enrich miR-3064-5p and target to inhibit IκBα as verified by exosome inhibitors and miR-3064-5p mimics and inhibitors. HPD elevates exosomal miR-3064-5p, macrophage exosomal miR-3064-5p, and inflammatory cytokine levels in mice circulation. PA PM-Exos from HPD-fed mice triggered inflammation in the circulation and metabolic tissues/organs of chow diet-fed mice. Overweight/obese individuals exhibit increased levels of circulating palmitoleic acid, exosomal miR-3064-5p, and high-sensitivity C-reactive proteins. CONCLUSIONS: Macrophage exosomes transferring miR-3064-5p to target IκBα and activate NF-κB signaling in metabolic cells is a mechanism of PA-induced metainflammation.

GnRH-mediated suppression of S100A4 expression inhibits endometrial epithelial cell proliferation in sheep via GNAI2/MAPK signaling.

Background: Gonadotrophin-releasing hormone (GnRH) administration significantly decreases the pregnancy rate of recipient ewes after embryo transfer, possibly because GnRH affects endometrial epithelial cell function. Therefore, this study investigated the effect of GnRH on endometrial epithelial cells. Methods: Transcriptome sequencing was used to determine the regulatory effect of GnRH on the ewe endometrium, and the S100A4 gene, which showed altered transcription, was screened as a candidate regulator of this effect. Endometrial epithelial cells were further isolated, the S100A4 protein was immunoprecipitated, and host proteins that interacted with S100A4 were identified by mass spectrometry. We further verified the effects of S100A4 and GNAI2 on the proliferation of endometrial epithelial cells via overexpression/knockdown experiments and subsequent CCK-8 and EdU assays. The effect of S100A4 deletion in endometrial cells on reproduction was verified in mice with S100A4 knockout. Results: Our results showed that S100A4 gene transcription in endometrial cells was significantly inhibited after GnRH administration. GNAI2 was identified as a downstream interacting protein of S100A4, and S100A4 was confirmed to activate the MAPK signaling pathway to promote cell proliferation by targeting GNAI2. Conclusion: GnRH can suppress the expression of S100A4 in the endometrium, consequently inhibiting the proliferation of endometrial cells through the S100A4/GNAI2/MAPK signaling pathway. These findings suggest a potential explanation for the limited efficacy of GnRH in promoting embryo implantation.

2D Exfoliation Chemistry Towards Covalent Pseudo-Layered Phosphate Framework Derived by Radical/Strain-Synergistical Process.

2D compounds exfoliated from weakly bonded bulk materials with van der Waals (vdW) interaction are easily accessible. However, the strong internal ionic/covalent bonding of most inorganic crystal frameworks greatly hinders 2D material exfoliation. Herein, we first proposed a radical/strain-synergistic strategy to exfoliate non-vdW interacting pseudo-layered phosphate framework. Specifically, hydroxyl radicals (⋅OH) distort the covalent bond irreversibly, meanwhile, H2O molecules as solvents, further accelerating interlayered ionic bond breakage but mechanical expansion. The innovative 2D laminar NASICON-type Na3V2(PO4)2O2F crystal, exfoliated by ⋅OH/H2O synergistic strategy, exhibits enhanced sodium-ion storage capacity, high-rate performance (85.7 mAh g-1 at 20 C), cyclic life (2300 cycles), and ion migration rates, compared with the bulk framework. Importantly, this chemical/physical dual driving technique realized the effective exfoliation for strongly coupled pseudo-layered frameworks, which accelerates 2D functional material development.

Multi-metal ions co-regulated vanadium oxide cathode toward long-life aqueous zinc-ion batteries.

Interlayer intercalation engineering shows great feasibility to improve the structure stability of the layered oxides. Although high Zn-storage capability has been attained based on the pillar effect of multifarious intercalants, an in-depth understanding the synergistic effect of intercalated multiple metal ions is still in deficiency. Herein, alkali metal ion K+, alkaline earth metal ion Mg2+ and trivalent metal ion Al3+ are introduced into the VO interlayer of V2O5. Due to the different electronegativity and hydrated ion radius of K+, Mg2+ and Al3+, adjusting the relative proportions of these metal ions can achieve an appropriate interlayer spacing, stable layer structure and regular morphology, which facilitates the transport kinetics of Zn2+. Under the synergistic effect of pre-intercalated multi-metal ion, the optimal tri-metal ion intercalated hydrated V2O5 cathode exhibits a high specific capacity of 382.4 mAh g-1 at 0.5 A g-1, and long-term cycling stability with capacity retention of 86 % after 2000 cycles at the high current density of 10 A g-1. Ex-situ and kinetic characterizations reveal the fast charge transfer and reversible Zn2+ intercalation mechanism. The multi-ion engineering strategy provides an effective way to design desirable layered cathode materials for aqueous zinc-ion batteries.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Rare earth elements induced electronic engineering in Rh cluster toward efficient alkaline hydrogen evolution reaction.

The unique electronic and crystal structures of rare earth metals (RE) offer promising opportunities for enhancing the hydrogen evolution reaction (HER) properties of materials. In this work, a series of RE (Sm, Nd, Pr and Ho)-doped Rh@NSPC (NSPC stands for N, S co-doped porous carbon nanosheets) with sizes less than 2 nm are prepared, utilizing a simple, rapid and solvent-free joule-heat pyrolysis method for the first time. The optimized Sm-Rh@NSPC achieves HER performance. The high-catalytic performance and stability of Sm-Rh@NSPC are attributed to the synergistic electronic interactions between Sm and Rh clusters, leading to an increase in the electron cloud density of Rh, which promotes the adsorption of H+, the dissociation of Rh-H bonds and the release of H2. Notably, the overpotential of the Sm-Rh@NSPC catalyst is a mere 18.1 mV at current density of 10 mAcm-2, with a Tafel slope of only 15.2 mV dec-1. Furthermore, it exhibits stable operation in a 1.0 M KOH electrolyte at 10 mA cm-2 for more than 100 h. This study provides new insights into the synthesis of composite RE hybrid cluster nanocatalysts and their RE-enhanced electrocatalytic performance. It also introduces fresh perspectives for the development of efficient electrocatalysts.

Direct and rapid thermal shock for recycling spent graphite in lithium-ion batteries.

Due to the rapid increase in the number of spent lithium-ion batteries, there has been a growing interest in the recovery of degraded graphite. In this work, a rapid thermal shock (RTS) strategy is proposed to regenerate spent graphite for use in lithium-ion batteries. The results of structural and morphological characterization demonstrate that the graphite is well regenerated by the RTS process. Additionally, an amorphous carbon layer forms and coats onto the surface of the graphite, contributing to excellent rate performance. The regenerated graphite (RG-1000) displays excellent rate performance, with capacities of 413 mAh g-1 at 50 mA g-1 and 102.1 mAh g-1 at 1000 mA g-1, respectively. Furthermore, it demonstrates long-term cycle stability, maintaining a capacity of 80 mAh g-1 at 1000 mA g-1 with a capacity retention of 78.4 % after 600 cycles. This RTS method enables rapid and efficient regeneration of spent graphite anodes for lithium-ion batteries, providing a facile and environmentally friendly strategy for their direct regeneration.

Enhanced redox kinetics in hierarchical tubular FeSe2 by incorporating Se quantum dots towards high-performance sodium-ion batteries.

Metal selenides have emerged as promising Na-storage anode materials owing to their substantial theoretical capacity and high cost-effectiveness. However, the application of metal selenides is hindered by inferior electronic conductivity, huge volume variation, and sluggish kinetics of ionic migration. In response to these challenges, herein, a hierarchical hollow tube consisting of FeSe2 nanosheets and Se quantum dots anchored within a carbon skeleton (HT-FeSe2/Se/C) is strategically engineered and synthesized. The most remarkable feature of HT-FeSe2/Se/C is the introduction of Se quantum dots, which could lead to high electron density near the Fermi level and significantly enhance the overall charge transfer capability of the electrode. Moreover, the distinctive hollow tubular structure enveloped by the carbon skeleton endows the HT-FeSe2/Se/C anode with robust structural stability and fast surface-controlled Na-storage kinetics. Consequently, the as-synthesized HT-FeSe2/Se/C demonstrates a reversible capacity of 253.5 mAh/g at a current density of 5 A/g and a high specific capacity of 343.9 mAh/g at 1 A/g after 100 cycles in sodium-ion batteries (SIBs). Furthermore, a full cell is assembled with HT-FeSe2/Se/C as the anode, and a vanadium-based cathode (Na3V2(PO4)2O2F), showcasing a high specific capacity of 118.1 mAh/g at 2 A/g. The excellent performance of HT-FeSe2/Se/C may hint at future material design strategies and advance the development and application of SIBs.

Prediction of Prostate Cancer Risk Stratification Based on A Nonlinear Transformation Stacking Learning Strategy.

PURPOSE: Prostate cancer (PCa) is an epithelial malignancy that originates in the prostate gland and is generally categorized into low, intermediate, and high-risk groups. The primary diagnostic indicator for PCa is the measurement of serum prostate-specific antigen (PSA) values. However, reliance on PSA levels can result in false positives, leading to unnecessary biopsies and an increased risk of invasive injuries. Therefore, it is imperative to develop an efficient and accurate method for PCa risk stratification. Many recent studies on PCa risk stratification based on clinical data have employed a binary classification, distinguishing between low to intermediate and high risk. In this paper, we propose a novel machine learning (ML) approach utilizing a stacking learning strategy for predicting the tripartite risk stratification of PCa. METHODS: Clinical records, featuring attributes selected using the lasso method, were utilized with 5 ML classifiers. The outputs of these classifiers underwent transformation by various nonlinear transformers and were then concatenated with the lasso-selected features, resulting in a set of new features. A stacking learning strategy, integrating different ML classifiers, was developed based on these new features. RESULTS: Our proposed approach demonstrated superior performance, achieving an accuracy of 0.83 and an area under the receiver operating characteristic curve value of 0.88 in a dataset comprising 197 PCa patients with 42 clinical characteristics. CONCLUSION: This study aimed to improve clinicians' ability to rapidly assess PCa risk stratification while reducing the burden on patients. This was achieved by using artificial intelligence-related technologies as an auxiliary method for diagnosing PCa.

Cation/Anion-Dual regulation in Na3MnTi(PO4)3 cathode achieves the enhanced electrochemical properties of Sodium-Ion batteries.

Na3MnTi(PO4)3 (NMTP) emerges as a promising cathode material with high-performance for sodium-ion batteries (SIBs). Nevertheless, its development has been limited by several challenges, including poor electronic conductivity, the Mn3+ Jahn-Teller effect, and the presence of a Na+/Mn2+ cation mixture. To address these issues, we have developed a cation/anion-dual regulation strategy to activate the redox reactions involving manganese, thereby significantly enhancing the performance of NMTP. This strategy simultaneously enhances the structural dynamics and facilitates rapid ion transport at high rates by inducing the formation of sodium vacancy. The combined effects of these modifications lead to a substantial improvement in specific capacity (79.1 mAh/g), outstanding high-rate capabilities (35.9 mAh/g at 10C), and an ultralong cycle life (only 0.040 % capacity attenuation per cycle over 250 cycles at 1C for Na3.34Mn1.2Ti0.8(PO3.98F0.02)3) when used as a cathode material in SIBs. Furthermore, its performance in full cell demonstrates impressive rate capability (44.4 mAh/g at 5C) and exceptional cycling stability (with only 0.116 % capacity decay per cycle after 150 cycles at 1C), suggesting its potential for practical applications. This work presents a dual regulation strategy targeting different sites, offering a significant advancement in the development of NASICON phosphate cathodes for SIBs.

Defect engineering unveiled: Enhancing potassium storage in expanded graphite anode.

Expanded graphite (EG) stands out as a promising material for the negative electrode in potassium-ion batteries. However, its full potential is hindered by the limited diffusion pathway and storage sites for potassium ions, restricting the improvement of its electrochemical performance. To overcome this challenge, defect engineering emerges as a highly effective strategy to enhance the adsorption and reaction kinetics of potassium ions on electrode materials. This study delves into the specific effectiveness of defects in facilitating potassium storage, exploring the impact of defect-rich structures on dynamic processes. Employing ball milling, we introduce surface defects in EG, uncovering unique effects on its electrochemical behavior. These defects exhibit a remarkable ability to adsorb a significant quantity of potassium ions, facilitating the subsequent intercalation of potassium ions into the graphite structure. Consequently, this process leads to a higher potassium voltage. Furthermore, the generation of a diluted stage compound is more pronounced under high voltage conditions, promoting the progression of multiple stage reactions. Consequently, the EG sample post-ball milling demonstrates a notable capacity of 286.2 mAh g-1 at a current density of 25 mA g-1, showcasing an outstanding rate capability that surpasses that of pristine EG. This research not only highlights the efficacy of defect engineering in carbon materials but also provides unique insights into the specific manifestations of defects on dynamic processes, contributing to the advancement of potassium-ion battery technology.

Transcriptome profiling reveals superovulation with the gonadotropin-releasing hormone agonist trigger impaired embryo implantation in mice.

Introduction: Superovulation is a critical step in assisted reproductive technology, but the use of human chorionic gonadotropin (hCG) as a trigger for superovulation can result in ovarian hyperstimulation. Thus, the use of Gonadotropin-releasing hormone agonist (GnRHa) trigger has been increasingly adopted, although it has been associated with a higher rate of pregnancy failure compared to natural cycles. This study aimed to investigate the effect of GnRHa trigger on embryo implantation in a mouse model. Methods: Mice in the superovulation (PG) group were administered 7.5 IU of PMSG, followed by the injection of 3.5 µg of GnRHa (Leuprorelin) 48 h later, while mice in the control group (CTR) mated naturally. We compared the number of oocytes, blastocysts, and corpus luteum between the two groups and the implantation sites after the transfer of natural blastocysts. Ovaries, uterus, and serum 2 and 4 days after mating were collected for qRT-PCR, transcriptome sequencing, and hormone assays. Results: The PG group had more oocytes, blastocysts, and corpus luteum after superovulation than the CTR group. However, the mRNA expression of leukemia inhibitory factor (Lif) and the number of implantation sites were reduced in the PG group. The ELISA assay revealed that superovulation increased ovarian estrogen secretion. The transcriptome analysis showed that superphysiological estrogen led to a response of the uterus to a high estrogen signal, resulting in abnormal endometrium and extracellular matrix remodeling and up-regulation of ion transport and inflammation-related genes. Conclusion: Our findings suggest that a combination of PMSG and GnRHa trigger impaired embryo implantation in mice, as the excessive uterine response to superphysiological estrogen levels can lead to the change of gene expression related to endometrial remodeling, abnormal expression of uterine ion transport genes and excessive immune-related genes.

Surface CN bonds mediate photocatalytic CO2 reduction into efficient CH4 production in TiO2-decorated g-C3N4 nanosheets.

Graphitic carbon nitride (g-C3N4, CN) has garnered considerable attention in the field of photocatalysis due to its favorable band gap and high specific surface area. However, its primary practical limitation lies in the strong radiative recombination of lone pair (LP) electronic states, leading to limited efficiency in separating photogenerated carriers and subsequently diminishing photocatalytic performance. In this study, we devised and synthesized a heterojunction photocatalytic system comprising TiO2 nanosheets supported on modified g-C3N4 (MCN), designated as MCN/TiO2. The presence of CN functional groups on the tri-s-triazine nitrogen captures photogenerated electrons by modifying LP electronic states, resulting in a reduction in the fluorescence emission intensity of g-C3N4. Simultaneously, it forms chemical bonds with the supported TiO2 nanosheets, creating an efficient electron transfer pathway for the accumulation of photogenerated electrons at the active Ti sites. Experimentally, the MCN/TiO2 photocatalytic system exhibited optimal performance in CO2 reduction. The CH4 production rate reached 26.59 µmol g-1 h-1, surpassing that of TiO2 and CN/TiO2 by approximately 8 and 3 times, respectively. Furthermore, this photocatalytic system demonstrated exceptional photostability over five cycles, each lasting 4 h. This research offers a valuable approach for the efficient separation and transfer of photogenerated carriers in composite materials based on g-C3N4.

Atomic Valence Reversal-Induced Polarization Resonance Spurs Highly Efficient Electromagnetic Wave Absorption in α-Fe2O3@Carbon Microtubes.

Variegation and complexity of polarization relaxation loss in many heterostructured materials provide available mechanisms to seek a strong electromagnetic wave (EMW) absorption performance. Here we construct a unique heterostructured compound that bonds α-Fe2O3 nanosheets of the (110) plane on carbon microtubes (CMTs). Through effective alignment between the Fermi energy level of CMTs and the conduction band position of α-Fe2O3 nanosheets at the interface, we attain substantial polarization relaxation loss via novel atomic valence reversal between Fe(III) ↔ Fe(III-) induced with periodic electron injection from conductive CMTs under EMW irradiation to give α-Fe2O3 nanosheets. Such heterostructured materials possess currently reported minimum reflection loss of -84.01 dB centered at 10.99 GHz at a thickness of 3.19 mm and an effective absorption bandwidth (reflection loss ≤ -10 dB) of 7.17 GHz (10.83-18 GHz) at 2.65 mm. This work provides an effective strategy for designing strong EMW absorbers by combining highly efficient electron injection and atomic valence reversal.

Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High-Voltage Barrier to Achieve High Energy Density and Long Life of Sodium-Ion Batteries.

The stable phase transformation during electrochemical progress drives extensive research on vanadium-based polyanions in sodium-ion batteries (SIBs), especially Na3V2(PO4)3 (NVP). And the electron transfer between V3+/4+ redox couple in NVP could be generally achieved, owing to the confined crystal variation during battery service. However, the more favorable V4+/5+ redox couple is still in hard-to-access situation due to the high barrier and further brings about the corresponding inefficiency in energy densities. In this work, the multilevel redox in NVP frame (MLNP) alters reaction pathway to undergo homeostatic solid solution process and breaks the high barrier of V4+/5+ at high voltage, taking by progressive transition metal (V, Fe, Ti, and Cr) redox couple. The diversified reaction paths across diffusion barriers could be realized by distinctive release/uptake of inactive Na1 site, confirmed by the calculations of density functional theory. Thereby its volume change is merely 1.73% during the multielectron-transfer process (≈2.77 electrons). MLNP cathode could achieve an impressive energy density of 440 Wh kg-1, driving the leading development of MLNP among other NASICON structure SIBs. The integration of multiple redox couples with low strain modulates the reaction pathway effectively and will open a new avenue for fabricating high-performance cathodes in SIBs.

Janus Binder Chemistry for Synchronous Enhancement of Iodine Species Adsorption and Redox Kinetics toward Sustainable Aqueous Zn-I2 Batteries.

Currently, the desired research focus in energy storage technique innovation has been gradually shifted to next-generation aqueous batteries holding both high performance and sustainability. However, aqueous Zn-I2 batteries have been deemed to have great sustainable potential, owing to the merits of cost-effective and eco-friendly nature. However, their commercial application is hindered by the serious shuttle effect of polyiodides during reversible operations. In this work, a Janus functional binder based on chitosan (CTS) molecules was designed and prepared; the polar terminational groups impart excellent mechanical robustness to hybrid binders; meanwhile, it can also deliver isochronous enhancement on physical adsorption and redox kinetics toward I2 species. By feat of highly effective remission to shuttle effect, the CTS cell exhibits superb electrochemical storage capacities with long-term robustness, specifically, 144.1 mAh g-1, at a current density of 0.2 mA g-1 after 1500 cycles. Simultaneously, the undesired self-discharging issue could be also well-addressed; the Coulombic efficiency could remain at 98.8 % after resting for 24 h. More importantly, CTS molecules endow good biodegradability and reusable properties; after iodine species were reloaded, the recycled devices could also deliver specific capacities of 73.3 mAh g-1, over 1000 cycles. This Janus binder provides a potential synchronous solution to realize high comprehensive performance with high iodine utilization and further make it possible for sustainable Zn-I2 batteries.

Linear and phase controllable terahertz frequency conversion via ultrafast breaking the bond of a meta-molecule.

The metasurface platform with time-varying characteristics has emerged as a promising avenue for exploring exotic physics associated with Floquet materials and for designing photonic devices like linear frequency converters. However, the limited availability of materials with ultrafast responses hinders their applications in the terahertz range. Here we present a time-varying metasurface comprising an array of superconductor-metal hybrid meta-molecules. Each meta-molecule consists of two meta-atoms that are "bonded" together by double superconducting microbridges. Through experimental investigations, we demonstrate high-efficiency linear terahertz frequency conversion by rapidly breaking the bond using a coherent ultrashort terahertz pump pulse. The frequency and relative phase of the converted wave exhibit strong dependence on the pump-probe delay, indicating phase controllable wave conversion. The dynamics of the meta-molecules during the frequency conversion process are comprehensively understood using a time-varying coupled mode model. This research not only opens up new possibilities for developing innovative terahertz sources but also provides opportunities for exploring topological dynamics and Floquet physics within metasurfaces.