ACS Nano最新文献

Concentrated electrolytes based on lithium bis(fluorosulfonyl)imide (LiFSI) have been proposed as an effective Li-compatible electrolyte for anode-free lithium metal batteries (AFLMBs). However, these electrolytes suffer from severe aluminum corrosion at an elevated potential. To address this issue, we propose a binary ionic liquid (IL) electrolyte additive comprising the 1-methyl-1-butyl pyrrolidinium cation (Pyr₁₄⁺), difluoro(oxalate)borate anion (DFOB^-), and difluorophosphate (PO₂F₂^-) anion to mitigate the Li inventory loss and Al corrosion in 4 M LiFSI/DME electrolyte simultaneously. On the anode side, the IL additive facilitates the formation of a robust Li₃N- and LiF-rich solid electrolyte interphase, promoting highly reversible Li plating/stripping and uniform Li deposition. Additionally, the ILs alter the Li⁺ solvation structure, leading to enhanced t_Li⁺ and rapid Li⁺ desolvation kinetics. Concurrently, on the cathode side, the ILs aid in the generation of dense LiF- and AlF-rich passivation films against Al corrosion. By using the IL-added electrolyte, the Cu||LiMn_0.7Fe_0.3PO₄ cell operates stably at 4.5 V, and the Cu||NCM613 cell with a high loading of 4.0 mA h cm^-2 sustains 142 cycles until 80% capacity retention. This research contributes to a deeper understanding of the IL additive mechanism at the electrode-electrolyte interfaces and offers a straightforward approach to designing practical high-voltage AFLMB electrolytes.

Pulmonary fibrosis (PF) is an interstitial lung disease tightly associated with the disruption of mitochondrial pool homeostasis, a delicate balance influenced by functional and dysfunctional mitochondria within lung cells. Mitochondrial transfer is an emerging technology to increase functional mitochondria via exogenous mitochondrial delivery; however, the therapeutic effect on mitochondrial transfer is hampered during the PF process by the persistence of dysfunctional mitochondria, which is attributed to impaired mitophagy. Herein, we reported engineering mitochondria mediated by mitophagy-enhanced nanoparticle (Mito-MEN), which promoted synchronal regulation of functional and dysfunctional mitochondria for treating PF. Mitophagy-enhanced nanoparticles (MENs) were fabricated through the encapsulation of Parkin mRNA, and the electrostatic interaction favored MENs to anchor isolated healthy mitochondria for the construction of Mito-MEN. Mito-MEN increased the load of functional exogenous mitochondria by enhancing mitochondrial delivery efficiency and promoted mitophagy of dysfunctional endogenous mitochondria. In a bleomycin (BLM)-induced PF mouse model, Mito-MEN repaired mitochondrial function and efficiently relieved PF-related phenotypes. This study provides a powerful tool for synchronal adjustment of mitochondrial pool homeostasis and offers a translational approach for pan-mitochondrial disease therapies.

Probing and manipulating the intriguing nonlinear optical responses in van der Waals (vdW) ferroelectrics offer opportunities for their applications in nanophotonics. Here, we report the observation of giant and tunable second-harmonic generation (SHG) in ferroelectric CuInP₂S₆ (CIPS) and CIPS/MoS₂ heterostructures. The results show that CIPS, ranging from multilayer to bulk-like samples, all exhibit strong SHG with giant anisotropy. The SHG anisotropy is attributed to the local strain along the a-axis that naturally exists in CIPS, as evidenced by piezoresponse force microscopy measurement. We further realized the strong modulation of SHG in CIPS by interfacing with monolayer MoS₂. A combination of polarization, temperature, and thickness-dependent SHG and photoluminescence analyses shows that the nonlinear optical signal control in CIPS/MoS₂ heterostructures is unrelated to the polar symmetry of CIPS and MoS₂ but is driven by light absorption-mediated interfacial coupling. Our study provides a material platform based on vdW ferroelectric heterostructures for achieving dynamic control of nonlinear optical responses, which shows great potential applications in modern nanophotonics.

Abstract: Immune thrombocytopenia (ITP) is a complicated bleeding disease characterized by a sharp platelet reduction. As a dominating element involved in ITP, megakaryocytes (MKs) are responsible for thrombopoiesis. However, the mechanism underlying the dysregulation of thrombopoiesis that occurs in ITP remains unidentified. In this study, we examined the role of Yes-associated protein 1 (YAP1) in thrombopoiesis during ITP. We observed reduced YAP1 expression with cytoskeletal actin misalignment in MKs from patients with ITP. Using an experimental ITP mouse model, we showed that reduced YAP1 expression induced aberrant MK distribution, reduced the percentage of late MKs among the total MKs, and caused submaximal platelet recovery. Mechanistically, YAP1 upregulation by binding of GATA-binding protein 1 to its promoter promoted MK maturation. Phosphorylated YAP1 promoted cytoskeletal activation by binding its WW2 domain to myosin heavy chain 9, thereby facilitating thrombopoiesis. Targeting YAP1 with its activator XMU-MP-1 was sufficient to rescue cytoskeletal defects and thrombopoiesis dysregulation in YAP1+/- mice with ITP and patients. Taken together, these results demonstrate the crucial role of YAP1 in thrombopoiesis, providing potential for the development of diagnostic markers and therapeutic options for ITP.

Developing alternative two-dimensional (2D) metallic/semiconducting (M/S) van der Waals heterostructures (vdWHs) along with an understanding of interfacial photocarrier behavior is crucial for designing high-performance optoelectronic devices. Here, we comprehensively explored the photophysical model of photocarrier generation and interfacial transfer in as-grown 2D 1T'/2H MoS₂ vdWHs using various spectroscopic characterizations. We demonstrated the transitions of activated photocarrier transfer trajectories by tuning the pump photon energies across the 2H MoS₂ bandgap. The importance of confined bilayer transfer systems and strong interlayer coupling at vdW interfaces for transfer efficiency was elucidated. Additionally, the fluorophlogopite substrate was found to be an external method for regulating photocarrier generation in individual 2H layers through the p-doping effect at the substrate-2H layer interfaces, and this influence was alleviated after introducing the 2H-1T' vdW interface. Particularly, 1T' MoS₂ as a broadband hot carrier absorber enabled the ultrafast (∼133 fs) injection and extraction of energetic hot carriers into the 2H layer via a photothermionic emission mechanism, achieving a high efficiency of ∼41% under 900 nm photoexcitation at room temperature. Our work offers fundamental insights into the complex interfacial carrier photophysics in 2D M/S vdWHs, providing a way of constructing advanced multifunctional devices by using these emerging materials as active components and interface engineering.

High-performance and durable anion exchange membranes (AEMs) are critical for realizing economical green hydrogen production through alkaline water electrolysis (AWE) or AEM water electrosysis (AEMWE). However, existing AEMs require sophisticated fabrication protocols and exhibit unsatisfactory electrochemical performance and long-term durability. Here we report an AEM fabricated via a one-pot, in situ interfacial Menshutkin reaction, which assembles a highly cross-linked polymer containing high-density quaternary ammoniums and nanovoids inside a reinforcing porous support. This structure endows the membrane with high anion-conducting ability, water uptake (but low swelling), and mechanical and thermochemical robustness. Consequently, the assembled membrane achieves excellent AWE (0.97 A cm^-2 at 1.8 V) and AEMWE (5.23 A cm^-2 at 1.8 V) performance at 5 wt % KOH and 80 °C, significantly exceeding that of commercial and previously developed membranes, and excellent long-term durability. Our approach provides an effective method for fabricating AEMs for various energy and environmental applications.

Nucleation is a fundamentally important step in electrochemical phase transition reactions, e.g., in electrodeposition, which is pertinent for emerging battery technology, nanoparticle synthesis, and many industrial processes. Surface defects have been suggested to enhance nucleation rates. However, directly quantifying the nucleation rates at specific surface sites is challenging due to the ensemble averaging effect in bulk measurements. Herein, we report the measurement of rates and energetics of electronucleation across the model surface of highly oriented pyrolytic graphite (HOPG). Specifically, scanning electrochemical cell microscopy (SECCM) is used to confine the nucleation spatially in the nanoscale cell, allowing one nucleation event to be measured at one time. The scanning capability further allows the mapping of Ag nucleation at the step edge vs basal plane. A stochastic model is developed to extract the nucleation rate and energetics from voltammetric experiments. We observed a ∼57 mV difference in the median nucleation overpotential between the step edge and basal plane, corresponding to a ∼12 kJ mol^-1 difference in the nucleation energy barrier. The voltammetric method to measure the nucleation rate explored here can be extended to understand the heterogeneity of nucleation rates in other electrochemical nucleation systems, e.g., metal anode batteries.

Abstract: In REACH4, a phase 1/2, open-label, single-arm, multicenter study, the pharmacokinetics (PK), efficacy, and safety of ruxolitinib were evaluated in treatment-naïve and steroid-refractory pediatric patients with grade 2 to 4 acute graft-versus-host disease (aGVHD; n = 45). Ruxolitinib dosing was based on age and targeted the exposure in adults receiving 10 mg twice daily; group 1 (aged ≥12 to <18 years) received 10 mg twice daily and preliminary starting doses for groups 2 (aged ≥6 to <12 years) and 3 (aged ≥2 to <6 years) were 5 mg twice daily and 4 mg/m2 twice daily, respectively. The phase 1 primary objective was to assess ruxolitinib PK parameters and define an age-appropriate recommended phase 2 dose (RP2D) for patients aged <12 years. The phase 2 primary objective was to measure the activity of ruxolitinib as assessed by overall response rate (ORR) at day 28; the key secondary objective was to assess the durable ORR at day 56. Ruxolitinib exposure was comparable across age groups; starting doses were confirmed as the RP2D. The median duration of ruxolitinib exposure was 3.8 months (range, 0.3-11.2). ORR in all patients was 84.4% (90% confidence interval [CI], 72.8-92.5) at day 28, with a durable ORR at day 56 of 66.7% (90% CI, 53.4-78.2); high response rates were observed across age groups and in both treatment-naïve and steroid-refractory subgroups. Adverse events were consistent with those expected in patients with aGVHD (anemia, decreased neutrophil and leukocyte count) treated with ruxolitinib. In pediatric patients with aGVHD, ruxolitinib showed clinically meaningful efficacy with no new safety signals. This trial was registered at www.clinicaltrials.gov as #NCT03491215.