Synergism of non-thermal plasma and low concentration RSL3 triggers ferroptosis via promoting xCT lysosomal degradation through ROS/AMPK/mTOR axis in lung cancer cells.

BACKGROUND: Though (1S, 3R)-RSL3 has been used widely in basic research as a small molecular inducer of ferroptosis, the toxicity on normal cells and poor pharmacokinetic properties of RSL3 limited its clinical application. Here, we investigated the synergism of non-thermal plasma (NTP) and low-concentration RSL3 and attempted to rise the sensitivity of NSCLC cells on RSL3. METHODS: CCK-8 assay was employed to detect the change of cell viability. Microscopy and flowcytometry were applied to identify lipid peroxidation, cell death and reactive oxygen species (ROS) level respectively. The molecular mechanism was inspected with western blot and RT-qPCR. A xenograft mice model was adopted to investigate the effect of NTP and RSL3. RESULTS: We found the synergism of NTP and low-concentration RSL3 triggered severe mitochondria damage, more cell death and rapid ferroptosis occurrence in vitro and in vivo. NTP and RSL3 synergistically induced xCT lysosomal degradation through ROS/AMPK/mTOR signaling. Furthermore, we revealed mitochondrial ROS was the main executor for ferroptosis induced by the combined treatment. CONCLUSION: Our research shows NTP treatment promoted the toxic effect of RSL3 by inducing more ferroptosis rapidly and provided possibility of RSL3 clinical application.

Manipulating the Microenvironment of Single Atoms by Switching Support Crystallinity for Industrial Hydrogen Evolution.

Modulating the microenvironment of single-atom catalysts (SACs) is critical to optimizing catalytic activity. Herein, we innovatively propose a strategy to improve the local reaction environment of Ru single atoms by precisely switching the crystallinity of the support from high crystalline and low crystalline, which significantly improves the hydrogen evolution reaction (HER) activity. The Ru single-atom catalyst anchored on low-crystalline nickel hydroxide (Ru-LC-Ni(OH)2 ) reconstructs the distribution balance of the interfacial ions due to the activation effect of metal dangling bonds on the support. Single-site Ru with a low oxidation state induces the aggregation of hydronium ions (H3 O+ ), leading to the formation of a local acidic microenvironment in alkaline media, breaking the pH-dependent HER activity. As a comparison, the Ru single-atom catalyst anchored on high-crystalline nickel hydroxide (Ru-HC-Ni(OH)2 ) exhibits a sluggish Volmer step and a conventional local reaction environment. As expected, Ru-LC-Ni(OH)2 requires low overpotentials of 9 and 136 mV at 10 and 1000 mA cm-2 in alkaline conditions and operates stably at 500 mA cm-2 for 500 h in an alkaline seawater anion exchange membrane (AEM) electrolyzer. This study provides a new perspective for constructing highly active single-atom electrocatalysts.

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 the FeCoNi/FeAl2O4 hybrid coating, 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.

Polarized Ultrathin BN Induced Dynamic Electron Interactions for Enhancing Acidic Oxygen Evolution.

Developing ruthenium-based heterogeneous catalysts with an efficient and stable interface is essential for enhanced acidic oxygen evolution reaction (OER). Herein, we report a defect-rich ultrathin boron nitride nanosheet support with relatively independent electron donor and acceptor sites, which serves as an electron reservoir and receiving station for RuO2, realizing the rapid supply and reception of electrons. Through precisely controlling the reaction interface, a low OER overpotential of only 180 mV (at 10 mA cm-2) and long-term operational stability (350 h) are achieved, suggesting potential practical applications. In situ characterization and theoretical calculations have validated the existence of a localized electronic recycling between RuO2 and ultrathin BN nanosheets (BNNS). The electron-rich Ru sites accelerate the adsorption of water molecules and the dissociation of intermediates, while the interconnection between the O-terminal and B-terminal edge establishes electronic back-donation, effectively suppressing the over-oxidation of lattice oxygen. This study provides a new perspective for constructing a stable and highly active catalytic interface.

Switching the Oxygen Evolution Mechanism on Atomically Dispersed Ru for Enhanced Acidic Reaction Kinetics.

Designing stable single-atom electrocatalysts with lower energy barriers is urgent for the acidic oxygen evolution reaction. In particular, the atomic catalysts are highly dependent on the kinetically sluggish acid-base mechanism, limiting the reaction paths of intermediates. Herein, we successfully manipulate the steric localization of Ru single atoms at the Co3O4 surface to improve acidic oxygen evolution by precise control of the anchor sites. The delicate structure design can switch the reaction mechanism from the lattice oxygen mechanism (LOM) to the optimized adsorbate evolution mechanism (AEM). In particular, Ru atoms embedded into cation vacancies reveal an optimized mechanism that activates the proton donor-acceptor function (PDAM), demonstrating a new single-atom catalytic pathway to circumvent the classic scaling relationship. Steric interactions with intermediates at the anchored Ru-O-Co interface played a primary role in optimizing the intermediates' conformation and reducing the energy barrier. As a comparison, Ru atoms confined to the surface sites exhibit a lattice oxygen mechanism for the oxygen evolution process. As a result, the delicate atom control of the spatial position presents a 100-fold increase in mass activity from 36.96 A gRu(ads)-1 to 4012.11 A gRu(anc)-1 at 1.50 V. These findings offer new insights into the precise control of single-atom catalytic behavior.

Activity-Stability Balance: The Role of Electron Supply Effect of Support in Acidic Oxygen Evolution.

Developing efficient and durable electrocatalysts for the oxygen evolution reaction (OER) in proton exchange membrane (PEM) electrolyzers represents a significant challenge. Herein, the cobalt-ruthenium oxide nano-heterostructures are successfully synthesized on carbon cloth (CoOx /RuOx -CC) for acidic OER through a simple and fast solution combustion strategy. The rapid oxidation process endows CoOx /RuOx -CC with abundant interfacial sites and defect structures, which enhances the number of active sites and the charge transfer at the electrolyte-catalyst interface, promoting the OER kinetics. Moreover, the electron supply effect of the CoOx support allows electrons to transfer from Co to Ru sites during the OER process, which is beneficial to alleviate the ion leaching and over-oxidation of Ru sites, improving the catalyst activity and stability. As a self-supported electrocatalyst, CoOx /RuOx -CC displays an ultralow overpotential of 180 mV at 10 mA cm-2 for OER. Notably, the PEM electrolyzer using CoOx /RuOx -CC as the anode can be operated at 100 mA cm-2 stably for 100 h. Mechanistic analysis shows that the strong catalyst-support interaction is beneficial to redistribute the electronic structure of RuO bond to weaken its covalency, thereby optimizing the binding energy of OER intermediates and lowering the reaction energy barrier.

P and Se Binary Vacancies and Heterostructures Modulated MoP/MoSe2 Electrocatalysts for Improving Hydrogen Evolution and Coupling Electricity Generation.

It is not enough to develop an ideal hydrogen evolution reaction (HER) electrocatalysts by single strategy. Here, the HER performances are significantly improved by the combined strategies of P and Se binary vacancies and heterostructure engineering, which is rarely explored and remain unclear. As a result, the overpotentials of MoP/MoSe2 -H heterostructures rich in P and Se binary vacancies are 47 and 110 mV at 10 mA cm-2 in 1 m KOH and 0.5 m H2 SO4 electrolytes, respectively. Especially, in 1 m KOH, the overpotential of MoP/MoSe2 -H is very close to commercial Pt/C at the beginning and even better than Pt/C when current density is over 70 mA cm-2 . The strong interactions between MoSe2 and MoP facilitate electrons transfer from P to Se. Thus, MoP/MoSe2 -H possesses more electrochemically active sites and faster charge transfer capability, which are all in favor of high HER activities. Additionally, Zn-H2 O battery with MoP/MoSe2 -H as cathode is fabricated for simultaneous generation of hydrogen and electricity, which displays the maximum power density of up to 28.1 mW cm-2 and stable discharging performance for 125 h. Overall, this work validates a vigorous strategy and provides guidance for the development of efficient HER electrocatalysts.

Association of RTN4 indel polymorphisms with the risk of tumorigenesis in the Chinese Han population.

Although studies have reported the association of two insertion/deletion (indel) polymorphisms in the 3'-untranslated region (UTR) of the RTN4 gene with the risk of tumorigenesis, the findings are inconsistent and require further explanation. Comprehensive literature searches were undertaken in Pubmed, Embase, Web of Science, China National Knowledge Infrastructure, and WangFang database. The risk of tumorigenesis was determined using odds ratios (ORs) and 95% confidence intervals (CIs) based on STATA 12.0 software. A total of four case-control studies with 1214 patients and 1850 controls focused on the RTN4 gene TATC/- polymorphism and five case-control studies with 1625 patients and 2321 controls on the RTN4 gene CAA/- polymorphism. Pooled analysis showed that the TATC/- polymorphism was not associated with the risk of tumorigenesis under all genetic models and the CAA/- polymorphism was significantly associated with the risk of tumorigenesis under the homozygote genetic model (Del/Del vs. Ins/Ins: OR=1.32, 95%CI=1.04-1.68, P=0.02). In conclusion, the current findings suggested that the CAA/- polymorphism in the 3'-UTR of the RTN4 gene was significantly associated with the risk of tumorigenesis in the Chinese population and may serve as a valuable marker for predicting tumor risk.

Ambient γ-Rays-Mediated Noble-Metal Deposition on Defect-Rich Manganese Oxide for Glycerol-Assisted H2 Evolution at Industrial-Level Current Density.

Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy-saving hydrogen production. Herein, we report an ambient and controllable γ-ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect-rich manganese oxides (M@MnO2-x , M=Ru, Pt, Pd, Ir) for glycerol-assisted H2 evolution. Benefiting from the strong penetrability of γ-rays, nanoparticles and defect supports are formed simultaneously and bridged by metal-oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru-O-Mn bonds activate the Ru and Mn sites in Ru@MnO2-x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm-2 in a continuous-flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2-x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect-rich MnO2 support promotes the dissociation of H2 O, while the defect-regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol-assisted hydrogen production.

MXene-Regulated Metal-Oxide Interfaces with Modified Intermediate Configurations Realizing Nearly 100% CO2 Electrocatalytic Conversion.

Electrocatalytic CO2 reduction via renewable electricity provides a sustainable way to produce valued chemicals, while it suffers from low activity and selectivity. Herein, we constructed a novel catalyst with unique Ti3 C2 Tx MXene-regulated Ag-ZnO interfaces, undercoordinated surface sites, as well as mesoporous nanostructures. The designed Ag-ZnO/Ti3 C2 Tx catalyst achieves an outstanding CO2 conversion performance of a nearly 100% CO Faraday efficiency with high partial current density of 22.59 mA cm-2 at -0.87 V versus reversible hydrogen electrode. The electronic donation of Ag and up-shifted d-band center relative to Fermi level within MXene-regulated Ag-ZnO interfaces contributes the high selectivity of CO. The CO2 conversion is highly correlated with the dominated linear-bonded CO intermediate confirmed by in situ infrared spectroscopy. This work enlightens the rational design of unique metal-oxide interfaces with the regulation of MXene for high-performance electrocatalysis beyond CO2 reduction.

Stabilizing Low-Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution.

Designing novel single-atom catalysts (SACs) supports to modulate the electronic structure is crucial to optimize the catalytic activity, but rather challenging. Herein, a general strategy is proposed to utilize the metalloid properties of supports to trap and stabilize single-atoms with low-valence states. A series of single-atoms supported on the surface of tungsten carbide (M-WCx , M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WCx , the single-atoms exhibit weak coordination with surface W and C atoms, resulting in the formation of low-valence active centers similar to metals. The unique metal-metal interaction effectively stabilizes the low-valence single atoms on the WCx surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru-WCx exhibits superior mass activities of 7.84 and 62.52 A mgRu -1 for the hydrogen oxidation and evolution reactions (HOR/HER), respectively. In-depth mechanistic analysis demonstrates that an ideal dual-sites cooperative mechanism achieves a suitable adsorption balance of Had and OHad , resulting in an energetically favorable Volmer step. This work offers new guidance for the precise construction of highly active SACs.

Clusters Induced Electron Redistribution to Tune Oxygen Reduction Activity of Transition Metal Single-Atom for Metal-Air Batteries.

Oxygen reduction reaction (ORR) activity can be effectively tuned by modulating the electron configuration and optimizing the chemical bonds. Herein, a general strategy to optimize the activity of metal single-atoms is achieved by the decoration of metal clusters via a coating-pyrolysis-etching route. In this unique structure, the metal clusters are able to induce electron redistribution and modulate M-N species bond lengths. As a result, M-ACSA@NC exhibits superior ORR activity compared with the nanoparticle-decorated counterparts. The performance enhancement is attributed to the optimized intermediates desorption benefiting from the unique electronic configuration. Theoretical analysis reinforces the significant roles of metal clusters by correlating the ORR activity with cluster-induced charge transfer. As a proof-of-concept, various metal-air batteries assembled with Fe-ACSA@NC deliver remarkable power densities and capacities. This strategy is an effective and universal technique for electron modulation of M-N-C, which shows great potential in application of energy storage devices.

Dual-Active Sites Engineering of N-Doped Hollow Carbon Nanocubes Confining Bimetal Alloys as Bifunctional Oxygen Electrocatalysts for Flexible Metal-Air Batteries.

Since the sluggish kinetic process of oxygen reduction (ORR)/evolution (OER) reactions, the design of highly-efficient, robust, and cost-effective catalysts for flexible metal-air batteries is desired but challenging. Herein, bimetallic nanoparticles encapsulated in the N-doped hollow carbon nanocubes (e.g., FeCo-NPs/NC, FeNi-NPs/NC, and CoNi-NPs/NC) are rationally designed via a general heat-treatment strategy of introducing NH3 pyrolysis of dopamine-coated metal-organic frameworks. Impressively, the resultant FeCo-NPs/NC hybrid exhibits superior bifunctional electrocatalytic performance for ORR/OER, manifesting exceptional discharging performance, outstanding lifespan, and prime flexibility for both Zn/Al-air batteries, superior to those of state-of-the-art Pt/C and RuO2 catalysts. X-ray absorption near edge structure and density functional theory indicate that the strong synergy between FeCo alloy and N-doped carbon frameworks has a distinctive activation effect on bimetallic Fe/Co atoms to synchronously modify the electronic structure and afford abundant dual-active Fe/Co-Nx sites, large surface area, high nitrogen doping level, and conductive carbon frameworks to boost the reversible oxygen electrocatalysis. Such N-doped carbon with bimetallic alloy bonds provides new pathways for the rational creation of high-efficiency energy conversion and storage equipment.

Electronic Modulation Caused by Interfacial Ni-O-M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution Kinetics.

Designing definite metal-support interfacial bond is an effective strategy for optimizing the intrinsic activity of noble metals, but rather challenging. Herein, a series of quantum-sized metal nanoparticles (NPs) anchored on nickel metal-organic framework nanohybrids (M@Ni-MOF, M=Ru, Ir, Pd) are rationally developed through a spontaneous redox strategy. The metal-oxygen bonds between the NPs and Ni-MOF guarantee structural stability and sufficient exposure of the surface active sites. More importantly, such precise interfacial feature can effectively modulate the electronic structure of hybrids through the charge transfer of the formed Ni-O-M bridge and then improves the reaction kinetics. As a result, the representative Ru@Ni-MOF exhibits excellent hydrogen evolution reaction (HER) activity at all pH values, even superior to commercial Pt/C and recent noble-metal catalysts. Theoretical calculations deepen the mechanism understanding of the superior HER performance of Ru@Ni-MOF through the optimized adsorption free energies of water and hydrogen due to the interfacial-bond-induced electron redistribution.

Controllable Design of MoS2 Nanosheets Grown on Nitrogen-Doped Branched TiO2 /C Nanofibers: Toward Enhanced Sodium Storage Performance Induced by Pseudocapacitance Behavior.

In this work, expanded MoS2 nanosheets grown on nitrogen-doped branched TiO2 /C nanofibers (NBT/C@MoS2 NFs) are prepared through electrospinning and hydrothermal treatment method as anode materials for sodium-ion batteries (SIBs). The continuous 1D branched TiO2 /C nanofibers provide a large surface area to grow expanded MoS2 nanosheets and enhance the electronic conductivity and cycling stability of the electrode. The large surface area and doping of nitrogen can facilitate the transfer of both Na+ ions and electrons. With the merits of these unique design and extrinsic pseudocapacitance behavior, the NBT/C@MoS2 NFs can deliver ultralong cycle stability of 448.2 mA h g-1 at 200 mA g-1 after 600 cycles. Even at a high rate of 2000 mA g-1 , a reversible capacity of 258.3 mA h g-1 can still be achieved. The kinetic analysis demonstrates that pseudocapacitive contribution is the major factor to achieve excellent rate performance. The rational design and excellent electrochemical performance endow the NBT/C@MoS2 NFs with potentials as promising anode materials for SIBs.

Acceptor-Doping Accelerated Charge Separation in Cu2 O Photocathode for Photoelectrochemical Water Splitting: Theoretical and Experimental Studies.

Cu2 O is a typical photoelectrocatalyst for sustainable hydrogen production, while the fast charge recombination hinders its further development. Herein, Ni2+ cations have been doped into a Cu2 O lattice (named as Ni-Cu2 O) by a simple hydrothermal method and act as electron traps. Theoretical results predict that the Ni dopants produce an acceptor impurity level and lower the energy barrier of hydrogen evolution. Photoelectrochemical (PEC) measurements demonstrate that Ni-Cu2 O exhibits a photocurrent density of 0.83 mA cm-2 , which is 1.34 times higher than that of Cu2 O. And the photostability has been enhanced by 7.81 times. Moreover, characterizations confirm the enhanced light-harvesting, facilitated charge separation and transfer, prolonged charge lifetime, and increased carrier concentration of Ni-Cu2 O. This work provides deep insight into how acceptor-doping modifies the electronic structure and optimizes the PEC process.

In Situ Fabrication of Branched TiO2 /C Nanofibers as Binder-Free and Free-Standing Anodes for High-Performance Sodium-Ion Batteries.

Herein, 1D free-standing and binder-free hierarchically branched TiO2 /C nanofibers (denoted as BT/C NFs) based on an in situ fabrication method as an anode for sodium-ion batteries are reported. The in situ fabrication endows this material with large surface area and strong structural stability, providing this material with abundant active sites and smooth channels for fast ion transportation. As a result, BT/C NFs with the character of free-standing membranes are directly used as binder-free anode for sodium-ion batteries, delivering a capacity of 284 mA h g-1 at a current density of 200 mA g-1 after 1000 cycles. Even at a high current density of 2000 mA g-1 , the reversible capacity can still achieve as high as 204 mA h g-1 . By means of kinetic analysis, it is demonstrated that the remarkable surface pseudocapacitive behavior is also a major factor to achieve excellent performance. The rationally designed structure coupled with the inherent pseudocapacitive behavior gives this material potential for sodium-ion batteries.

Carbon-Based Alloy-Type Composite Anode Materials toward Sodium-Ion Batteries.

In the scenario of renewable clean energy gradually replacing fossil energy, grid-scale energy storage systems are urgently necessary, where Na-ion batteries (SIBs) could supply crucial support, due to abundant Na raw materials and a similar electrochemical mechanism to Li-ion batteries. The limited energy density is one of the major challenges hindering the commercialization of SIBs. Alloy-type anodes with high theoretical capacities provide good opportunities to address this issue. However, these anodes suffer from the large volume expansion and inferior conductivity, which induce rapid capacity fading, poor rate properties, and safety issues. Carbon-based alloy-type composites (CAC) have been extensively applied in the effective construction of anodes that improved electrochemical performance, as the carbon component could alleviate the volume change and increase the conductivity. Here, state-of-the-art CAC anode materials applied in SIBs are summarized, including their design principle, characterization, and electrochemical performance. The corresponding alloying mechanism along with its advantages and disadvantages is briefly presented. The crucial roles and working mechanism of the carbon matrix in CAC anodes are discussed in depth. Lastly, the existing challenges and the perspectives are proposed. Such an understanding critically paves the way for tailoring and designing suitable alloy-type anodes toward practical applications.

Necklace-like Multishelled Hollow Spinel Oxides with Oxygen Vacancies for Efficient Water Electrolysis.

The durability and reactivity of catalysts can be effectively and precisely controlled through the careful design and engineering of their surface structures and morphologies. Herein, we develop a novel "adsorption-calcination-reduction" strategy to synthesize spinel transitional metal oxides with a unique necklace-like multishelled hollow structure exploiting sacrificial templates of carbonaceous microspheres, including NiCo2O4 (NCO), CoMn2O4, and NiMn2O4. Importantly, benefiting from the unique structures and reduction treatment to offer rich oxygen vacancies, the unique reduced NCO (R-NCO) as a bifunctional electrocatalyst exhibits the dual characteristics of good stability as well as high electrocatalytic activity for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). At 1.61 V cell voltage, a 10 mA cm-2 water splitting current density is obtained from the dual-electrode, alkaline water electrolyzer. Calculations based on density functional theory (DFT) reveal a mechanism for the promotion of the catalytic reactions based on a decrease in the energy barrier for the formation of intermediates resulting from the introduction of oxygen vacancies through the reduction process. This method could prove to be an effective general strategy for the preparation of complex, hollow structures and functionalities.

In Situ Fabrication of Hierarchically Branched TiO2 Nanostructures: Enhanced Performance in Photocatalytic H2 Evolution and Li-Ion Batteries.

1D branched TiO2 nanomaterials play a significant role in efficient photocatalysis and high-performance lithium ion batteries. In contrast to the typical methods which generally have to employ epitaxial growth, the direct in situ growth of hierarchically branched TiO2 nanofibers by a combination of the electrospinning technique and the alkali-hydrothermal process is presented in this work. Such the branched nanofibers exhibit improvement in terms of photocatalytic hydrogen evolution (0.41 mmol g-1 h-1 ), in comparison to the conventional TiO2 nanofibers (0.11 mmol g-1 h-1 ) and P25 (0.082 mmol g-1 h-1 ). Furthermore, these nanofibers also deliver higher lithium specific capacity at different current densities, and the specific capacity at the rate of 2 C is as high as 201. 0 mAh g-1 , roughly two times higher than that of the pristine TiO2 nanofibers.