ACS Earth and Space Chemistry最新文献

Intercalation engineering is a promising strategy to promote zinc-ion storage of layered cathodes; however, is impeded by the complex fabrication routes and inert electrochemical behaviors of intercalators. Herein, an organic imidazole intercalation strategy is proposed, where V₂O₅ and NH₄V₃O₈ (NVO) model materials are adopted to verify the feasibility of the imidazole intercalator in improving the zinc storage capabilities of vanadium-based cathodes. The intercalated imidazole molecules could not only expand interlayer spacing and strengthen structural stability by serving as extra “pillars” but also provide extra coordination sites for zinc storage via the coordination reaction between Zn²⁺ and the C═N group. This gives rise to a dual-mode ion storage mechanism and favorable electrochemical performances. As a result, imidazole-intercalated V₂O₅ delivers a capacity of 179.9 mAh g^–1 after 5000 cycles at 20 A g^–1, while the imidazole-intercalated NVO harvests a high capacity output of 170.2 mAh g^–1 after 700 cycles at 2 A g^–1. This work is anticipated to boost the application potentials of vanadium-based cathodes in aqueous zinc-ion batteries.

Although tumor immunotherapy has achieved significant success in recent years, tackling solid tumors remains a formidable challenge. Here, we present an approach that utilizes outer membrane vesicles (OMVs) from bacterial cells as scaffolds to engage immune cells in solid tumor immunotherapy. Two types of nanobodies targeting CD47/SIRPα and PD-1/PD-L1 pathways were simultaneously conjugated onto the surfaces of the OMVs in divalent and trivalent forms using orthogonal SpyCatcher-SpyTag and SnoopCatcher-SnoopTag chemistry. This resulted in the generation of an OMV-based nanosized immune cell engager (OMV-NICE) with dual-targeting abilities. In vitro assays confirmed the retention of the function of the two nanobodies on the OMV-NICE, as evidenced by the synergistically enhanced macrophage phagocytosis and T cell cytotoxicity against tumor cells. In vivo studies using a B16-F10 melanoma mouse model also revealed the superior antitumor activity of OMV-NICE compared to those of unconjugated nanobodies and OMVs alone. Subsequent mechanistic investigations further supported the enhanced recruitment of macrophages and T cells to the tumor region by OMV-NICE. Overall, this work expands the current repertoire of immune cell engagers, and the developed OMV-NICE platform holds great promise for broad applications, particularly in solid tumor immunotherapy.

The most recent breakthrough in state-of-the-art electronics and optoelectronics involves the adoption of steep-slope field-effect transistors (FETs), promoting sub-60 mV/dec subthreshold swing (SS) at ambient temperature, effectively overcoming “Boltzmann limit” to minimize power consumption. Here, a series integration of nanoscale copper-based resistive-filamentary threshold switch (TS) with the IGZO channel-based FET is used to develop a TS-FET, in which the turn-on characteristics exhibit an abrupt transition over five decades, with an extremely low SS of 7 mV/dec, a high on/off ratio (>10⁹), and ultralow leakage current (40-fold decrease), ensuring excellent repeatability and device yield. Unlike previous device-centric studies, this work highlights potential circuit applications (logic-inverter, pulse-sensor amplification, and photodetector) based on TS-FET. The sharp transition behavior of TS-FET enables the establishment of logic inverters with a high voltage gain of ≈800, with a circuit-level demonstration achieving a bias-independent record-high intrinsic gain (>1000). A wearable pulse sensor integrated with an amplifier circuit ensured the precise amplification of electrophysical signals by 450 times. In addition, the application of a TS-FET-based photodetector features high responsivity (1.08 × 10⁴ mA/W) and detectivity (1.03 × 10²⁰ Jones). The low-power strategy of TS-FETs is promising for the development of energy-efficient integrated circuits alongside sensor-interconnected biomedical applications in wearable technology.

Lead-halide perovskite nanocrystals (NCs) have gained significant attention for their promising applications in lighting and display technologies. However, blue-emitting NCs have struggled to match the high efficiency of their red and green counterparts. Moreover, many reported blue-emitting perovskite NCs contain heavy metal lead (Pb), which poses risks to human health and the environment. In this study, we synthesized rare-earth-based Cs₃TmCl₆ NCs via the hot injection method, which exhibit a broadband blue emission at 440 nm. Combined experimental and theoretical studies indicate that the broadband emission in Cs₃TmCl₆ arises from self-trapped excitons due to the excited-state structural distortion of the [TmCl₆]^3– cluster. Furthermore, the ultrafast dynamics of charge carriers were analyzed using time-resolved photoluminescence and transient absorption measurements. Encouraged by the remarkable thermal, light, and water stabilities of Cs₃TmCl₆ NCs, as evidenced by experimental and theoretical results, a white light-emitting diode was further designed and fabricated using the Cs₃TmCl₆ NCs as the color converter. The device exhibits outstanding performance, achieving a long half-lifetime of 336 h and a large color-rendering index of 87.0. Combining eco-friendly features and a facile synthesis method, the rare-earth-based Cs₃TmCl₆ NCs mark a significant breakthrough as a reliable blue emitter, showcasing their future potential in lighting and display applications.

Boron carbide (B_4+δC) possesses a large potential as a structural material owing to its lightness, refractory character, and outstanding mechanical properties. However, its large-scale industrialization is set back by its tendency to amorphize when subjected to an external stress. In the present work, we design a path toward nanostructured boron carbide with greatly enhanced hardness and resistance to amorphization. The reaction pathway consists of triggering an isomorphic transformation of covalent nanocrystals of Na_1–xB_5–xC_1+x (x = 0.18) produced in molten salts. The resulting 10 nm B_4.1C nanocrystals exhibit a 4-fold decrease of size compared to previous works. Solid-state ¹¹B and ¹³C NMR coupled to density functional theory (DFT) reveal that the boron carbide nanocrystals are made of a complex mixture of atomic configurations, which are located at the covalent structural chains between B₁₁C icosahedral building units. These nanocrystals are combined with a spark plasma-sintering-derived method operated at high pressure. This yields full densification while maintaining the particle size. The nanoscaled grains and high density of grain boundaries provide the resulting nanostructured bodies with significantly enhanced hardness and resistance to amorphization, thus delivering a superhard material.

Magnetic adatoms on superconductors give rise to Yu-Shiba-Rusinov (YSR) states that hold considerable interest for the design of topological superconductivity. Here, we show that YSR states are also an ideal platform to engineer structures with intricate wave function symmetries. We assemble structures of iron atoms on the quasi-two-dimensional superconductor 2H-NbSe₂. The Yu-Shiba-Rusinov wave functions of individual atoms extend over several nanometers enabling hybridization even at large adatom spacing. We show that the substrate can be exploited to deliberately break symmetries of the adatom structure leading to hybridized YSR states exhibiting symmetries that cannot be found in orbitals of iso-structural planar molecules in the gas phase. We exploit this potential by designing chiral YSR wave functions of triangular adatom structures. Our results significantly expand the range of interesting quantum states that can be engineered using arrays of magnetic adatoms on superconductors.

Tissue nanotransfection (TNT)-based fluorescent labeling of cell-specific exosomes has shown that exosomes play a central role in physiological keratinocyte–macrophage (mϕ) crosstalk at the wound-site. Here, we report that during the early phase of wound reepithelialization, macrophage-derived exosomes (Exo_mϕ), enriched with the outer mitochondrial membrane protein TOMM70, are localized in leading-edge keratinocytes. TOMM70 is a 70 kDa adaptor protein anchored in the mitochondrial outer membrane and plays a critical role in maintaining mitochondrial function and quality. TOMM70 selectively recognizes cytosolic chaperones by its tetratricopeptide repeat (TPR) domain and facilitates the import of preproteins lacking a positively charged mitochondrial targeted sequence. Exosomal packaging of TOMM70 in mϕ was independent of mitochondrial fission. TOMM70-enriched Exo_mϕ compensated for the hypoxia-induced depletion of epidermal TOMM70, thereby rescuing mitochondrial metabolism in leading-edge keratinocytes. Thus, macrophage-derived TOMM70 is responsible for the glycolytic ATP supply to power keratinocyte migration. Blockade of exosomal uptake from keratinocytes impaired wound closure with the persistence of proinflammatory mϕ in the wound microenvironment, pointing toward a bidirectional crosstalk between these two cell types. The significance of such bidirectional crosstalk was established by the observation that in patients with nonhealing diabetic foot ulcers, TOMM70 is deficient in keratinocytes of wound-edge tissues.

Most of the biological interfaces are curved. Understanding the organizational structures and interaction patterns at such curved biointerfaces is therefore crucial not only for deepening our comprehension of the principles that govern life processes but also for designing and developing targeted drugs aimed at diseased cells and tissues. Despite the considerable efforts dedicated to this area of research, our understanding of curved biological interfaces is still limited. Many aspects of these interfaces remain elusive, presenting both challenges and opportunities for further exploration. In this review, we summarize the structural characteristics of biological interfaces found in nature, the current research status of materials associated with curved biointerfaces, and the theoretical advancements achieved to date. Finally, we outline future trends and challenges in the theoretical and technological development of curved biointerfaces. By addressing these challenges, people could bridge the knowledge gap and unlock the full potential of curved biointerfaces for scientific and technological advancements, ultimately benefiting various fields and improving human health and well-being.

In utero gene editing with mRNA-based therapeutics has the potential to revolutionize the treatment of neurodevelopmental disorders. However, a critical bottleneck in clinical application has been the lack of mRNA delivery vehicles that can efficiently transfect cells in the brain. In this report, we demonstrate that in utero intracerebroventricular (ICV) injection of densely PEGylated lipid nanoparticles (ADP-LNPs) containing an acid-degradable PEG–lipid can safely and effectively deliver mRNA for gene editing enzymes to the fetal mouse brain, resulting in successful transfection and editing of brain cells. ADP-LNPs containing Cre mRNA transfected 30% of the fetal brain cells in Ai9 mice and had no detectable adverse effects on fetal development and postnatal growth. In addition, ADP-LNPs efficiently transfected neural stem and progenitor cells in Ai9 mice with Cre mRNA, which subsequently proliferated and caused over 40% of the cortical neurons and 60% of the hippocampal neurons to be edited in treated mice 10 weeks after birth. Furthermore, using Angelman syndrome, a paradigmatic neurodevelopmental disorder, as a disease model, we demonstrate that ADP-LNPs carrying Cas9 mRNA and gRNA induced indels in 21% of brain cells within 7 days postpartum, underscoring the precision and potential of this approach. These findings demonstrate that LNP/mRNA complexes have the potential to be a transformative tool for in utero treatment of neurodevelopmental disorders and set the stage for a frontier in treating neurodevelopmental disorders that focuses on curing genetic diseases before birth.

The low ionic conductivity of poly(ethylene oxide) (PEO)-based polymer electrolytes at room temperature impedes their practical applications. The addition of a plasticizer into polymer electrolytes could significantly promote ion transport while inevitably decreasing their mechanical strength. Herein, we report a supramolecular plasticizer (SMP) to break the trade-off effect between ionic conductivity and mechanical properties in PEO-based polymer electrolytes. Accordingly, the SMP is constructed by tetraethylene glycol dimethyl ether (G4) and SbF₃ through halogen bonds. The SMP-plasticized PEO electrolyte (PEO/SMP) presents a simultaneously enhanced ionic conductivity of 2.4 × 10^–4 S cm^–1 (25 °C) and a high mechanical strength of 8.1 MPa, compared to those of pristine PEO-based electrolytes. Benefiting from the halogen bonds between G4 and SbF₃, the Li–O coordination in PEO/SMP is evidently weakened, and thus rapid Li⁺ transport is achieved. Furthermore, the PEO/SMP electrolyte possesses a wide electrochemical stability window of 4.5 V and, importantly, derives an inorganic-rich SEI with a low interfacial resistance on a lithium metal surface. By using PEO/SMP, the lithium-metal battery with the LiNi_0.5Co_0.2Mn_0.3O₂ cathode exhibits a good rate and long-term cycling performance with a capacity retention of 75.3% (500 cycles). This work offers a rational guideline for the design of polymer electrolytes suitable for high-performance lithium-metal batteries.