Extendable piezo/ferroelectricity in nonstoichiometric 2D transition metal dichalcogenides.

Engineering piezo/ferroelectricity in two-dimensional materials holds significant implications for advancing the manufacture of state-of-the-art multifunctional materials. The inborn nonstoichiometric propensity of two-dimensional transition metal dichalcogenides provides a spiffy ready-available solution for breaking inversion centrosymmetry, thereby conducing to circumvent size effect challenges in conventional perovskite oxide ferroelectrics. Here, we show the extendable and ubiquitous piezo/ferroelectricity within nonstoichiometric two-dimensional transition metal dichalcogenides that are predominantly centrosymmetric during standard stoichiometric cases. The emerged piezo/ferroelectric traits are aroused from the sliding of van der Waals layers and displacement of interlayer metal atoms triggered by the Frankel defects of heterogeneous interlayer native metal atom intercalation. We demonstrate two-dimensional chromium selenides nanogenerator and iron tellurides ferroelectric multilevel memristors as two representative applications. This innovative approach to engineering piezo/ferroelectricity in ultrathin transition metal dichalcogenides may provide a potential avenue to consolidate piezo/ferroelectricity with featured two-dimensional materials to fabricate multifunctional materials and distinguished multiferroic.

Unlocking Liquid Sulfur Chemistry for Fast-Charging Lithium-Sulfur Batteries.

A recent study of liquid sulfur produced in an electrochemical cell has prompted further investigation into regulating Li-S oxidation chemistry. In this research, we examined the liquid-to-solid sulfur transition dynamics by visually observing the electrochemical generation of sulfur on a graphene-based substrate. We investigated the charging of polysulfides at various current densities and discovered a quantitative correlation between the size and number density of liquid sulfur droplets and the applied current. However, the areal capacities exhibited less sensitivity. This observation offers valuable insights for designing fast-charging sulfur cathodes. By incorporating liquid sulfur into Li-S batteries with a high sulfur loading of 4.2 mg cm-2, the capacity retention can reach ∼100%, even when increasing the rate from 0.1 to 3 C. This study contributes to a better understanding of the kinetics involved in the liquid-solid sulfur growth in Li-S chemistry and presents viable strategies for optimizing fast-charging operations.

Proteome-wide Mendelian randomization implicates nephronectin as an actionable mediator of the effect of obesity on COVID-19 severity.

Obesity is a major risk factor for Coronavirus disease (COVID-19) severity; however, the mechanisms underlying this relationship are not fully understood. As obesity influences the plasma proteome, we sought to identify circulating proteins mediating the effects of obesity on COVID-19 severity in humans. Here, we screened 4,907 plasma proteins to identify proteins influenced by body mass index using Mendelian randomization. This yielded 1,216 proteins, whose effect on COVID-19 severity was assessed, again using Mendelian randomization. We found that an s.d. increase in nephronectin (NPNT) was associated with increased odds of critically ill COVID-19 (OR = 1.71, P = 1.63 × 10-10). The effect was driven by an NPNT splice isoform. Mediation analyses supported NPNT as a mediator. In single-cell RNA-sequencing, NPNT was expressed in alveolar cells and fibroblasts of the lung in individuals who died of COVID-19. Finally, decreasing body fat mass and increasing fat-free mass were found to lower NPNT levels. These findings provide actionable insights into how obesity influences COVID-19 severity.

Stable Liquid-Sulfur Generation on Transition-Metal Dichalcogenides toward Low-Temperature Lithium-Sulfur Batteries.

The electrochemical formation of liquid sulfur at room temperature on the basal plane of MoS2 has attracted much attention due to the high areal capacity and rapid kinetics of lithium-liquid sulfur chemistry. However, the liquid sulfur is converted to the solid phase once it contacts the solid sulfur crystals generated from the edge of MoS2. Thus, stable liquid sulfur cannot be formed on the entire MoS2 surface. Herein, we report entire liquid sulfur generation on hydrogen-annealed MoS2 (H2-MoS2), even under harsh conditions of large overpotentials and low working temperatures. The origins of the solely liquid sulfur formation are revealed to be the weakened interactions between H2-MoS2 and sulfur molecules and the decreased electrical polarization on the edges of the H2-MoS2. Progressive nucleation and droplet-merging growth behaviors are observed during the sulfur formation on H2-MoS2, signifying high areal capacities by releasing active H2-MoS2 surfaces. To demonstrate the universality of this strategy, other transition-metal dichalcogenides (TMDs) annealed in hydrogen also exhibit similar sulfur growth behaviors. Furthermore, the H2 annealing treatment can induce sulfur vacancies on the basal plane and partial oxidation on the edge of TMDs, which facilitates liquid sulfur formation. Finally, liquid sulfur can be generated on H2-MoS2 flakes at an ultralow temperature of -50 °C, which provides a possible development of low-temperature lithium-sulfur batteries. This work demonstrates the potential of a pure liquid sulfur-lithium electrochemical system using functionalized two-dimensional materials.

Ultrastable and High Energy Calcium Rechargeable Batteries Enabled by Calcium Intercalation in a NASICON Cathode.

Ca-ion batteries (CIBs) have been considered a promising candidate for the next-generation energy storage technology owing to the abundant calcium element and the low reduction potential of Ca2+ /Ca. However, the large size and divalent nature of Ca2+ induce significant volume change and sluggish ion mobility in intercalation cathodes, leading to poor reversibly and low energy/power densities for CIBs. Herein, a polyanionic Na superionic conduction (NASICON)-typed Na-vacant Na1 V2 (PO4 )2 F3 (N1 PVF3 ) with sufficient interstitial spaces is reported as ultra-stable and high-energy Ca ion cathodes. The N1 PVF3 delivers exceptionally high Ca storage capacities of 110 and 65 mAh g-1 at 10 and 500 mA g-1 , respectively, and a record-long cyclability of 2000 cycles. More interestingly, by tailoring the fluorine content in N1 PVFx (1 ≤ x ≤ 3), the high working potential of 3.5 V versus Ca2+ /Ca is achievable. In conjunction with Ca metal anode and a compatible electrolyte, Ca metal batteries with N1 VPF3 cathodes are constructed, which deliver an initial energy density of 342 W h kg-1 , representing one of the highest values thus far reported for CIBs. Origins of the uncommonly stable and high-power capabilities for N1 PVF3 are elucidated as the small volume changes and low cation diffusion barriers among the cathodes.

Endogenous regulation of the Akt pathway by the aryl hydrocarbon receptor (AhR) in lung fibroblasts.

The aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor known to mediate toxic responses to dioxin. However, the role of the AhR in the regulation of cellular physiology has only recently been appreciated, including its ability to control cell cycle progression and apoptosis by unknown mechanisms. We hypothesized that the AhR enhances the activation of the AKT serine/threonine kinase (Akt) pathway to promote cell survival. Utilizing AhR knock-out (Ahr-/-) and wild-type (Ahr+/+) mouse lung fibroblasts (MLFs), we found that Ahr-/- MLFs have significantly higher basal Akt phosphorylation but that AhR did not affect Akt phosphorylation in MLFs exposed to growth factors or AhR ligands. Basal Akt phosphorylation was dependent on PI3K but was unaffected by changes in intracellular glutathione (GSH) or p85α. There was no significant decrease in cell viability in Ahr-/- MLFs treated with LY294002-a PI3K inhibitor-although LY294002 did attenuate MTT reduction, indicating an affect on mitochondrial function. Using a mass spectrometry (MS)-based approach, we identified several proteins that were differentially phosphorylated in the Ahr-/- MLFs compared to control cells, including proteins involved in the regulation of extracellular matrix (ECM), focal adhesion, cytoskeleton remodeling and mitochondrial function. In conclusion, Ahr ablation increased basal Akt phosphorylation in MLFs. Our results indicate that AhR may modulate the phosphorylation of a variety of novel proteins not previously identified as AhR targets, findings that help advance our understanding of the endogenous functions of AhR.

The aryl hydrocarbon receptor reduces LC3II expression and controls endoplasmic reticulum stress.

The aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor whose physiological function is poorly understood. The AhR is highly expressed in barrier organs such as the skin, intestine, and lung. The lungs are continuously exposed to environmental pollutants such as cigarette smoke (CS) that can induce cell death mechanisms such as apoptosis, autophagy, and endoplasmic reticulum (ER) stress. CS also contains toxicants that are AhR ligands. We have previously shown that the AhR protects against apoptosis, but whether the AhR also protects against autophagy or ER stress is not known. Using cigarette smoke extract (CSE) as our in vitro surrogate of environmental tobacco exposure, we first assessed the conversion of LC3I to LC3II, a classic feature of both autophagic and ER stress-mediated cell death pathways. LC3II was elevated in CSE-exposed lung structural cells [mouse lung fibroblasts (MLFs), MLE12 and A549 cells] when AhR was absent. However, this heightened LC3II expression could not be explained by increased expression of key autophagy genes (Gabarapl1, Becn1, Map1lc3b), upregulation of upstream autophagic machinery (Atg5-12, Atg3), or impaired autophagic flux, suggesting that LC3II may be autophagy independent. This was further supported by the absence of autophagosomes in Ahr-/- lung cells. However, Ahr-/- lung cells had widespread ER dilation, elevated expression of the ER stress markers CHOP and GADD34, and an accumulation of ubiquitinated proteins. These findings collectively illustrate a novel role for the AhR in attenuating ER stress by a mechanism that may be autophagy independent.

Exceptional catalytic effects of black phosphorus quantum dots in shuttling-free lithium sulfur batteries.

Lithium sulfur batteries with high energy densities are promising next-generation energy storage systems. However, shuttling and sluggish conversion of polysulfides to solid lithium sulfides limit the full utilization of active materials. Physical/chemical confinement is useful for anchoring polysulfides, but not effective for utilizing the blocked intermediates. Here, we employ black phosphorus quantum dots as electrocatalysts to overcome these issues. Both the experimental and theoretical results reveal that black phosphorus quantum dots effectively adsorb and catalyze polysulfide conversion. The activity is attributed to the numerous catalytically active sites on the edges of the quantum dots. In the presence of a small amount of black phosphorus quantum dots, the porous carbon/sulfur cathodes exhibit rapid reaction kinetics and no shuttling of polysulfides, enabling a low capacity fading rate (0.027% per cycle over 1000 cycles) and high areal capacities. Our findings demonstrate application of a metal-free quantum dot catalyst for high energy rechargeable batteries.

Hydrogen atom induced magnetic behaviors in two-dimensional materials: insight on origination in the model of α-MoO3.

Atomic layered two-dimensional (2D) materials have become fascinating research topics due to their intriguing performances, but the limitation of nonmagnetic properties hinders their further applications. Developing versatile strategies endowing 2D materials with ferromagnetism is one of the main trends in current research studies. Herein, a hydrogen plasma strategy is introduced to dope hydrogen (H) atoms into the prototypical layered α-MoO3 nanosheets, by which ferromagnetic and exchange bias (EB) effects can be induced by H atom doping into α-MoO3 to form HxMoO3. These effects were interpreted by density functional theory (DFT) calculations. We find that H atom doping can introduce unoccupied states and induce a net magnetic moment localized on the d orbital of the Mo atom, because of the generated asymmetric distribution of electronic states on the Mo atom near the Fermi level. Moreover, the saturation magnetization and the EB field (He) of hydrogenated α-MoO3 are found to be tunable through altering the amount of H dopant. This work provides new perspectives for the effective manipulation of ferromagnetism and exchange interaction through H doping. We hope that the presented hydrogenation strategy is applicable for other kinds of 2D materials.