Regulation of anion-Na+ coordination chemistry in electrolyte solvates for low-temperature sodium-ion batteries.

High-performance sodium storage at low temperature is urgent with the increasingly stringent demand for energy storage systems. However, the aggravated capacity loss is induced by the sluggish interfacial kinetics, which originates from the interfacial Na+ desolvation. Herein, all-fluorinated anions with ultrahigh electron donicity, trifluoroacetate (TFA-), are introduced into the diglyme (G2)-based electrolyte for the anion-reinforced solvates in a wide temperature range. The unique solvation structure with TFA- anions and decreased G2 molecules occupying the inner sheath accelerates desolvation of Na+ to exhibit decreased desolvation energy from 4.16 to 3.49 kJ mol-1 and 24.74 to 16.55 kJ mol-1 beyond and below -20 °C, respectively, compared with that in 1.0 M NaPF6-G2. These enable the cell of Na||Na3V2(PO4)3 to deliver 60.2% of its room-temperature capacity and high capacity retention of 99.2% after 100 cycles at -40 °C. This work highlights regulation of solvation chemistry for highly stable sodium-ion batteries at low temperature.

Quenching singlet oxygen via intersystem crossing for a stable Li-O2 battery.

Aprotic Li-O2 batteries are a promising energy storage technology, however severe side reactions during cycles lead to their poor rechargeability. Herein, highly reactive singlet oxygen (1O2) is revealed to generate in both the discharging and charging processes and is deterimental to battery stability. Electron-rich triphenylamine (TPA) is demonstrated as an effective quencher in the electrolyte to mitigate 1O2 and its associated parasitic reactions, which has the tertiary amine and phenyl groups to manifest excellent electrochemical stability and chemical reversibility. It reacts with electrophilic 1O2 to form a singlet complex during cycles, and it then quickly transforms to a triplet complex through nonradiative intersystem crossing (ISC). This efficiently accelerates the conversion of 1O2 to the ground-state triplet oxygen to eliminate its derived side reactions, and the regeneration of TPA. These enable the Li-O2 battery with obviously reduced overvoltages and prolonged lifetime for over 310 cycles when coupled with a RuO2 catalyst. This work highlights the ISC mechanism to quench 1O2 in Li-O2 battery.

Sustainable Aqueous Batteries Based on Bipolar Dissociation of Aluminum Hydroxyacetate Electrolyte.

Rechargeable aqueous batteries are potential systems for large-scale energy storage due to their high safety and low cost. However, developing aqueous batteries with high sustainability, affordability, and reversibility is urgent and challenging. Here we report an amphoteric aluminum hydroxyacetate (AlAc(OH)2) electrolyte with the ability of bipolar ionization of H+ and OH-, which facilitates the redox reactions at both the anthraquinone (AQ) anode and nickel hydroxide (Ni(OH)2) cathode. The bipolar ionization ability of the AlAc(OH)2(H2O)3 solvation structure results from the strong polarization ability of Al3+ and OH-. The H+/OH- dissociation ability with a dissociation constant of 5.0/3.0 is stronger than that of water (14.0), which boosts the simultaneous stable redox reactions of electrodes. Specifically, H+ uptake prevents the AQ anode from the formation of an ionic bond, suppressing the electrode dissolution, whereas OH- provides the local alkaline environment for the stable conversion reaction of the Ni(OH)2 cathode. The AQ anode in the designed AQ||Ni(OH)2 battery delivers a discharge capacity of 243.9 mAh g-1 and a capacity retention of 78.2% after 300 cycles with high reversibility. Moreover, a pouch cell with a discharge capacity of 0.90 Ah was assembled, exhibiting an energy density of 44.7 Wh kg-1 based on the total mass of the battery. This work significantly widens the types of aqueous batteries and represents a design philosophy of bipolar electrolytes and distinct electrochemical reactions with H+ and OH-.

Emerging strategies for treating autoimmune disease with genetically modified dendritic cells.

Gene editing of living cells has become a crucial tool in medical research, enabling scientists to address fundamental biological questions and develop novel strategies for disease treatment. This technology has particularly revolutionized adoptive transfer cell therapy products, leading to significant advancements in tumor treatment and offering promising outcomes in managing transplant rejection, autoimmune disorders, and inflammatory diseases. While recent clinical trials have demonstrated the safety of tolerogenic dendritic cell (TolDC) immunotherapy, concerns remain regarding its effectiveness. This review aims to discuss the application of gene editing techniques to enhance the tolerance function of dendritic cells (DCs), with a particular focus on preclinical strategies that are currently being investigated to optimize the tolerogenic phenotype and function of DCs. We explore potential approaches for in vitro generation of TolDCs and provide an overview of emerging strategies for modifying DCs. Additionally, we highlight the primary challenges hindering the clinical adoption of TolDC therapeutics and propose future research directions in this field.

Facilitating endoscopic full-thickness resection for gastric submucosal tumors with a novel snare traction method (with video).

BACKGROUND AND AIM: Endoscopic full-thickness resection (EFTR) is a promising technique in treating gastric submucosal tumors originating from the muscularis propria (SMT-MPs). However, it is challenging without counter-traction. METHODS: A snare was inserted through the forceps channel to grasp the part of the tumor or the mucosa connected to the tumor. The outer sheath and inner wire of snare in vitro were fixed by a pair of hemostatic forceps. The handle of snare was cut off, and the endoscope was pulled out without affecting the traction state of snare. Snare-assisted EFTR (EFTR-S) was then performed with counter-traction. One hundred and four patients with gastric SMT-MPs who received the procedure of EFTR with or without snare traction method were retrospectively analyzed using univariate and multiple regressions, and covariates were adjusted in the multiple analysis. RESULTS: Compared with EFTR group (n = 36), EFTR-S group (n = 68) showed a higher operative success rate (95.6% vs 72.2%, P = 0.001), a lower incidence of intraoperative hemorrhage (4.4% vs 16.7%, P = 0.038) and shorter operative time among operative successes (53.6 ± 16.6 min vs 67.7 ± 33.4 min, P < 0.001). Univariate logistic analysis showed that snare traction represented a significant factor, which could improve operative successful rate (odds ratio, 8.3; 95% confidence interval, 2.1 to 32.7; P = 0.002). Postoperative outcomes and adverse events among operative successes were similar between the two groups. CONCLUSIONS: This novel snare traction method may provide an effective counter-traction and reduce the difficulty of EFTR for gastric SMT-MPs.

Surface plasmon mediates the visible light-responsive lithium-oxygen battery with Au nanoparticles on defective carbon nitride.

Aprotic lithium-oxygen (Li-O2) batteries have gained extensive interest in the past decade, but are plagued by slow reaction kinetics and induced large-voltage hysteresis. Herein, we use a plasmonic heterojunction of Au nanoparticle (NP)-decorated C3N4 with nitrogen vacancies (Au/NV-C3N4) as a bifunctional catalyst to promote oxygen cathode reactions of the visible light-responsive Li-O2 battery. The nitrogen vacancies on NV-C3N4 can adsorb and activate O2 molecules, which are subsequently converted to Li2O2 as the discharge product by photogenerated hot electrons from plasmonic Au NPs. While charging, the holes on Au NPs drive the reverse decomposition of Li2O2 with a reduced applied voltage. The discharge voltage of the Li-O2 battery with Au/NV-C3N4 is significantly raised to 3.16 V under illumination, exceeding its equilibrium voltage, and the decreased charge voltage of 3.26 V has good rate capability and cycle stability. This is ascribed to the plasmonic hot electrons on Au NPs pumped from the conduction bands of NV-C3N4 and the prolonged carrier life span of Au/NV-C3N4 This work highlights the vital role of plasmonic enhancement and sheds light on the design of semiconductors for visible light-mediated Li-O2 batteries and beyond.

Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries.

Electrolytes that can ensure the movement of ions and regulate interfacial chemistries for fast mass and charge transfer are essential in many types of electrochemical energy storage devices. However, in the emerging energy-dense lithium-based batteries, the uncontrollable side-reactions and consumption of the electrolyte result in poor electrochemical performances and severe safety concerns. In this case, fluorination has been demonstrated to be one of the most effective strategies to overcome the above-mentioned issues without significantly contributing to engineering and technical difficulties. Herein, we present a comprehensive overview of the fluorinated solvents that can be employed in lithium-based batteries. Firstly, the basic parameters that dictate the properties of solvents/electrolytes are elaborated, including physical properties, solvation structure, interface chemistry, and safety. Specifically, we focus on the advances and scientific challenges associated with different solvents and the enhancement in their performance after fluorination. Secondly, we discuss the synthetic methods for new fluorinated solvents and their reaction mechanisms in depth. Thirdly, the progress, structure-performance relationship, and applications of fluorinated solvents are reviewed. Subsequently, we provide suggestions on the solvent selection for different battery chemistries. Finally, the existing challenges and further efforts on fluorinated solvents are summarized. The combination of advanced synthesis and characterization approaches with the assistance of machine learning will enable the design of new fluorinated solvents for advanced lithium-based batteries.

New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li-O2 Batteries.

Aprotic Li-O2 battery has attracted considerable interest for high theoretical energy density, however the disproportionation of the intermediate of superoxide (O2 - ) during discharge and charge leads to slow reaction kinetics and large voltage hysteresis. Herein, the chemically stable ruthenium tris(bipyridine) (RB) cations are employed as a soluble catalyst to alternate the pathway of O2 - disproportionation and its kinetics in both the discharge and charge processes. RB captures O2 - dimer and promotes their intramolecular charge transfer, and it decreases the energy barrier of the disproportionation reaction from 7.70 to 0.70 kcal mol-1 . This facilitates the discharge and charge processes and simultaneously mitigates O2 - and singlet oxygen related side reactions. These endow the Li-O2 battery with reduced discharge/charge voltage gap of 0.72 V and prolonged lifespan for over 230 cycles when coupled with RuO2 catalyst. This work highlights the vital role of superoxide disproportionation for Li-O2 battery.

Surface Coordination Modulated Morphological Anisotropic Engineering of Iron-Benzoquinone Frameworks for Lithium-Ion Batteries.

Morphological anisotropic engineering is powerful to synthesize metal-organic frameworks (MOFs) with versatile physicochemical properties for diverse applications ranging from gas storage/separation to electrocatalysis and batteries, etc. Herein, we developed a carbon substrate guided strategy to manipulate the facet-dependent coordination for morphology engineering of Fe-THBQ (tetrahydroxy-1,4-benzoquinone) frameworks, which is built with cubic Fe octamer bridged by two parallel THBQ ligands along three orthogonal axes, extending to a three-dimensional (3D) framework with pcu-e network topology. The electronegative O-containing functional groups on carbon surfaces compete with THBQ linkers to selectively interact with the unsaturated coordinated Fe cations on the {111} facets and inhibit crystal growth along the <111> direction. The morphology of Fe-THBQ evolves from thermodynamically favored truncated cube to cuboctahedron depending on the content of O-containing functional groups on the carbon substrate. The Fe-THBQ with varied morphologies exhibits facet-dependent performances for electrochemical lithium storage. This work will shed light on the morphology modulation of MOFs for promising applications.

Negative Lattice Expansion in an O3-Type Transition-Metal Oxide Cathode for Highly Stable Sodium-Ion Batteries.

The sodium extraction/insertion in layered transition-metal oxide (TMO) cathode materials are typically accompanied by slab sliding and lattice changes, leading to microstructure destruction and capacity decay. Herein, negative lattice expansion is observed in an O3 type Ni-based layered cathode of Na0.9 Ni0.32 Zn0.08 Fe0.1 Mn0.3 Ti0.2 O2 upon Na+ extraction. It is attributed to the weak Zn2+ -O2- orbital hybridization and increased electron density of the surrounding oxygen for reinforced interlayer O-O repulsive force. This enables gliding of TMO slabs for the intergrowth phase transition of P3→OP2 to alleviate lattice strain with moderate lattice shrinkage, which exhibits general interslab spacings and volume changes as low as 2.4 % and 1.9 %, respectively. The strong Ti-O bonds accommodate the internal distortion of TMO6 octahedra due to the flexibility of TiO6 octahedra during cycling. These endow a high specific capacity of 144.9 mAh g-1 and excellent cycling performance of pouch-type sodium-ion batteries with 93 % capacity retention after 3600 cycles.

Interfacial Engineering for Oriented Crystal Growth toward Dendrite-Free Zn Anode for Aqueous Zinc Metal Battery.

Zn deposition with a surface-preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag-modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP-Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion-resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high-performance aqueous zinc metal batteries.

Regulating Ion-Dipole Interactions in Weakly Solvating Electrolyte towards Ultra-Low Temperature Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are recognized as promising energy storage devices. However, they suffer from rapid capacity decay at ultra-low temperatures due to high Na+ desolvation energy barrier and unstable solid electrolyte interphase (SEI). Herein, a weakly solvating electrolyte (WSE) with decreased ion-dipole interactions is designed for stable sodium storage in hard carbon (HC) anode at ultra-low temperatures. 2-methyltetrahydrofuran with low solvating power is incorporated into tetrahydrofuran to regulate the interactions between Na+ and solvents. The reduced Na+-dipole interactions facilitate more anionic coordination in the first solvation sheath, which consistently maintains anion-enhanced solvation structures from room to low temperatures to promote inorganic-rich SEI formation. These enable WSE with a low freezing point of -83.3 °C and faster Na+ desolvation kinetics. The HC anode thus affords reversible capacities of 243.2 and 205.4 mAh g-1 at 50 mA g-1 at -40 and -60 °C, respectively, and the full cell of HC||Na3V2(PO4)3 yields an extended lifespan over 250 cycles with high capacity retention of ~100 % at -40 °C. This work sheds new lights on the ion-dipole regulation for ultra-low temperature SIBs.

Reversible Metal and Ligand Redox Chemistry in Two-Dimensional Iron-Organic Framework for Sustainable Lithium-Ion Batteries.

Metal-organic frameworks (MOFs) are emerging as attractive electrode materials for lithium-ion batteries, owing to their fascinating features of sustainable resources, tunable chemical components, flexible molecular skeletons, and renewability. However, they are faced with a limited number of redox-active sites and unstable molecular frameworks during electrochemical processes. Herein, we design a novel two-dimensional (2D) iron(III)-tetraamino-benzoquinone (Fe-TABQ) with dual redox centers of Fe cations and TABQ ligands for high-capacity and stable lithium storage. It is constructed of square-planar Fe-N2O2 linkages and phenylenediamine building blocks, between which the Fe-TABQ chains are connected by multiple hydrogen bonds, and then featured as an extended π-d-conjugated 2D structure. The redox chemistry of both Fe3+ cations and TABQ anions is revealed to render its remarkable specific capacity of 251.1 mAh g-1. Benefiting from the intrinsic robust Fe-N(O) bonds and reinforced Li-N(O) bonds during cycling, Fe-TABQ delivers high capacity retentions over 95% after 200 cycles at various current densities. This work will enlighten more investigations for the molecular designs of advanced MOF-based electrode materials.

Homeostatic Solid Solution in Layered Transition-Metal Oxide Cathodes of Sodium-Ion Batteries.

Two-phase transformation reaction is ubiquitous in solid-state electrochemistry; however, it usually involves inferior structure rearrangement upon extraction and insertion of large-sized Na+, thus leading to severe local strain, cracks, and capacity decay in sodium-ion batteries (SIBs). Here, a homeostatic solid solution reaction is reported in the layered cathode material P'2-Na0.653Ni0.081Mn0.799Ti0.120O2 during sodiation and desodiation. It is induced by the synergistic incorporation of Ni and Ti for the reinforced O(2p)-Mn(3d-eg*) hybridization, which leads to mitigated Jahn-Teller distortion of MnO6 octahedra, contracted transition-metal oxide slabs, and enlarged Na layer spacings. The thermodynamically favorable solid solution pathway rewards the SIBs with excellent cycling stability (87.2% capacity retention after 500 cycles) and rate performance (100.5 mA h g-1 at 2500 mA g-1). The demonstrated reaction pathway will open a new avenue for rational designing of cathode materials for SIBs and beyond.

Whole-Voltage-Range Solid-Solution Reaction in Layered Oxide Cathode of Sodium-Ion Batteries.

Layered manganese-based oxides (LMOs) are promising cathode materials for sodium-ion batteries (SIBs) due to their versatile structures. However, the Jahn-Teller effect of Mn3+ induces severe distortion of MnO6 octahedra, and the resultant low symmetry is responsible for the gliding of MnO2 layers and then inferior multiple-phase transitions upon Na+ extraction/insertion. Here, hexagonal P2-Na0.643 Li0.078 Mn0.827 Ti0.095 O2 is synthesized through the incorporation of Li and Ti into the distorted orthorhombic P'2-Na0.67 MnO2 to function as a phase-transition-free oxide cathode. It is revealed that Li in both the transition-metal and Na layers enhances the covalency of Mn-O bonds and allows degeneracy of Mn 3d eg orbitals to favor the formation of hexagonal phase, and the high strength of Ti-O bonds reduces the electrostatic interaction between Na and O for suppressed Na+ /vacancy rearrangements. These collectively lead to a whole-voltage-range solid-solution reaction between 1.8 and 4.3 V with a small volume variation of 1.49%. This rewards its excellent cycling stability (capacity retention of 90% after 500 cycles) and rate capability (89 mAh g-1 at 2000 mA g-1 ).

Application of methyl jasmonate to control chilling tolerance of postharvest fruit and vegetables: a meta-analysis and eliciting metabolism review.

Chilling injury is one of the most significant limitations for low temperature storage of postharvest fruits and vegetables, causing quality deterioration and economic loss. Increasing studies indicated that methyl jasmonate (MeJA) is critical in regulating the postharvest fruit and vegetables chilling tolerance. Based on a meta-analysis, the review analyzed the action of exogenous MeJA application on the chilling index in postharvest fruit and vegetables and summarized MeJA's mechanisms for controlling postharvest chilling injury. The meta-analysis found that MeJA treatment remarkably inhibited postharvest fruit and vegetable chilling injury. Moreover, we concluded the following function mechanism of MeJA on postharvest fruit and vegetable chilling tolerance: (1) Enhancing membrane integrity and energy supply, (2) Increasing antioxidant activity, (3) Enhancing arginine pathway, (4) Enhancing sugar metabolism, (5) Regulating phenolic metabolism, (6) Activating CBF pathway, (7) Regulating HSP accumulation and expression, and (8) Crosstalk with phytohormone. Finally, we summarized the regulatory mechanisms of MeJA on postharvest fruit and vegetable biological processes at the transcriptional and post-translational levels.

circ_0000337 Promotes the Progression of Cervical Cancer by miR-155-5p/RAB3B Axis.

Current study aims to investigate the biological function of circular RNA (circRNA, circ_0000337) in cervical cancer (CC). Bioinformatic analyses were used to predict targets for circ_0000337 and miR-155-5p, and analyze the gene expression differences between cervical squamous cell carcinoma and endocervical adenocarcinoma (CESC) tissues and normal tissues. Quantitative real-time polymerase chain reaction (qRT-PCR) and Western blot were applied to assess mRNA and protein expressions of circ_0000337, microRNA-155-5p (miR-155-5p) and member RAS oncogene family (RAB3B), respectively. Following the establishment of gain/loss-of-function models, CCK-8 was performed to evaluate cell proliferation. Bioinformatics analysis, dual-luciferase reporter assay and RNA immunoprecipitation (RIP) were used to identify the interaction in circ_0000337, miR-155-5p, and RAB3B. Circ_0000337 and RAB3B were upregulated, while miR-155-5p was downregulated in CC tissues and cell lines. circ_0000337 overexpression promoted cell proliferation, circ_0000337 knock down inhibited cell proliferation by sponging miR-155-5p. RAB3B was a target of miR-155-5p which was positively regulated by circ_0000337. In the collected CC tissues, there was a negative correlation between miR-155-5p and circ_0000337 or RAB3B, and a positive correlation between circ_0000337 and RAB3B. miR-155-5p was positively, while RAB3B was negatively correlated with OS in patients with CC, and they were negatively correlated. In conclusion, circ_0000337 upregulates RAB3B by sponging miR-155-5p to promote CC cell proliferation.

MicroRNA-182-5p aggravates ulcerative colitis by inactivating the Wnt/ß-catenin signaling pathway through DNMT3A-mediated SMARCA5 methylation.

This research focused on novel molecular mechanisms underlying microRNA (miR)-182-5p in ulcerative colitis (UC). Colon tissues were obtained from UC patients, and dextrose sodium sulfate (DSS)-induced mouse and interleukin-1ß (IL-1ß)-induced Caco-2 cell models were generated. Then, miR-182-5p, SMARCA5, and the Wnt/ß-catenin signaling pathway were altered in IL-1ß-stimulated Caco-2 cells and DSS-treated mice to assess their function. MiR-182-5p and SMARCA5 were upregulated and DNMT3A, ß-catenin, and Cyclin D1 were downregulated in UC patients, IL-1ß-stimulated Caco-2 cells, and DSS-treated mice. Mechanistically, miR-182-5p targeted DNMT3A to upregulate SMARCA5, thus blocking the Wnt/ß-catenin signaling pathway. Moreover, SMARCA5 silencing or Wnt/ß-catenin signaling pathway activation repressed apoptosis and augmented proliferation and epithelial barrier function of IL-1ß-stimulated Caco-2 cells. SMARCA5 silencing annulled the impacts of miR-182-5p overexpression on IL-1ß-stimulated Caco-2 cells. SMARCA5 silencing or miR-182-5p inhibition ameliorated intestinal barrier dysfunction in DSS-treated mice. Collectively, miR-182-5p aggravates UC by inactivating the Wnt/ß-catenin signaling pathway through DNMT3A-mediated SMARCA5 methylation.

Photoelectrochemistry of oxygen in rechargeable Li-O2 batteries.

Rechargeable lithium-oxygen (Li-O2) batteries are promising energy storage devices due to their high theoretical energy density. However, the sluggish kinetics of the oxygen reduction and evolution reactions (ORR/OER) at the cathodes results in large polarization and low energy efficiency. Although advances have been achieved in electrode material designs and battery configurations, large discharge/charge voltage gaps remain. The introduction of light into Li-O2 batteries has been demonstrated to boost the reaction kinetics of the ORR/OER, leading to enhanced electrochemical performances, but the understanding of the photoelectrochemical process at oxygen cathodes is limited. This tutorial review focuses on the recent findings regarding photoinvolved oxygen cathodes, battery configurations, and the stability of Li-O2 batteries, aiming to provide a fundamental understanding of photoinvolved Li-O2 batteries. The challenges and perspectives are discussed in light of the interdisciplinary nature of photochemistry, materials chemistry, electrochemistry, computation, spectroscopy, and surface science.

Emerging Lithiated Organic Cathode Materials for Lithium-Ion Full Batteries.

Organic electrode materials have application potential in lithium batteries owing to their high capacity, abundant resources, and structural designability. However, most reported organic cathodes are at oxidized states (namely unlithiated compounds) and thus need to couple with Li-rich anodes. In contrast, lithiated organic cathode materials could act as a Li reservoir and match with Li-free anodes such as graphite, showing great promise for practical full-battery applications. Here we summarize the synthesis, stability, and battery applications of lithiated organic cathode materials, including synthetic methods, stability against O2 and H2 O in air, and strategies to improve comprehensive electrochemical performance. Future research should be focused on new redox chemistries and the construction of full batteries with lithiated organic cathodes and commercial anodes under practical conditions. This Minireview will encourage more efforts on lithiated organic cathode materials and finally promote their commercialization.