Nanoscale Horizons最新文献

Ligand-assisted precursor engineering has emerged as an effective strategy to regulate the crystallization of metal halide perovskites. However, molecular-level design principles governing ligand-precursor interactions during early precursor evolution remain poorly understood. Here, using formamidinium lead iodide (FAPbI₃) as a model system, we establish an electronic-structure-driven framework to elucidate how functional ligands modify Pb-I precursor coordination through the interplay of lone-pair donation and π-electron distribution. Density functional theory (DFT) calculations were employed to systematically investigate a series of mono- and bifunctional ligands, including phenethylammonium chloride (PEA), 3-phenylpropionic acid (PPA), L-phenylalanine hydrochloride (PhA), and their conjugation-engineered derivatives. Enthalpic analysis shows that strong ligand-PbI₂ coordination is competitive with formation of the ligand-free FAI-PbI₂ adduct, while subsequent FAI association with ligand-bound PbI₂ yields stable ternary precursor complexes. Charge distribution, electrostatic potential mapping, interaction region analysis, and energy decomposition collectively demonstrate that moderate π participation can enhance ligand-PbI₂ binding through dispersion interactions, whereas direct π conjugation can weaken overall coordination by altering donor-site electronic structure and/or reducing favorable dispersion interactions through structural rigidification. Notably, bifunctional ligands exhibit multidentate coordination that provides enhanced enthalpic stabilization of ligand-bound precursor complexes. These findings provide molecular-level insights into ligand-regulated perovskite precursor evolution and offer rational guidelines for designing functional additives toward high-quality perovskite films.

Intracranial pressure (ICP) is a key physiological parameter for the diagnosis and management of traumatic brain injury, hydrocephalus, stroke, and other neurological disorders. ICP sensors are typically required to provide accurate pressure measurement at low pressure while maintaining long-term stability in biofluid environments. Although conventional liquid-based ICP systems remain the clinical standard, their bulky and tethered configurations increase the risk of infection and tissue injury and restrict patient mobility. Advances in miniaturized implantable sensors have created new opportunities for continuous and ambulatory ICP monitoring. This review summarizes recent developments in implantable ICP sensing technologies, covering sensing mechanisms, materials, designs, and fabrication processes. Wireless communication approaches together with emerging transient bioresorbable ICP sensors designed that eliminate the need for surgical removal are also discussed. Finally, the review highlights the remaining technical challenges and outlines future research directions toward long-term, minimally invasive ICP monitoring systems.

Aqueous zinc-ion hybrid capacitors (ZIHCs) hold great promise for safe and cost-effective energy storage, yet their practical viability is largely constrained by the insufficient ion-storage capacity of carbonaceous cathodes. Herein, we report a synergistic template-activation strategy to engineer hierarchically porous carbon from coal tar pitch, using zinc citrate as a dual-function self-sacrificial template in conjunction with KOH activation. During pyrolysis, zinc citrate undergoes a distinctive decomposition process in which the in situ generated ZnO nanoparticles serve as a removable hard template, while the concomitantly released gaseous species (CO₂, H₂O, and hydrocarbons) physically blow and chemically etch the carbon matrix. This cooperative mechanism simultaneously creates an interconnected micro-/meso-/macroporous architecture and implants abundant oxygen-containing functionalities, circumventing the need for exogenous templates or post-synthetic surface modification. The optimized ZCPC-1 cathode features a high specific surface area of 1922.1 m² g^-1 and an optimal balance of pore hierarchy and surface polarity. In aqueous ZIHCs, it delivers a reversible capacity of 171.2 mAh g^-1 at 0.2 A g^-1, an energy density of 167.85 Wh kg^-1, and outstanding long-term durability with 82.9% capacity retention over 25 000 cycles. Beyond aqueous systems, the quasi-solid-state flexible device assembled with PASHE gel electrolyte demonstrates a high capacity of 124.54 mAh g^-1 at 0.2 A g^-1, retains 80.5% of its initial capacity after 50 000 cycles at 10 A g^-1, and exhibits an ultralow self-discharge rate of 4.75 mV h^-1, underscoring its practical potential for flexible electronics. This work establishes a conceptually novel and industrially viable approach to upgrading low-cost coal tar pitch into high-performance carbon cathodes through in situ defect engineering and surface chemistry modulation, offering new perspectives for advanced aqueous energy storage systems.

Two-dimensional (2D) semiconductor nanosheets (NSs) provide an atomically precise platform for photocatalysis. In this study, we utilize silver (Ag) photodeposition (PD) to spatially resolve the photocatalytic activity of titania NSs, uncovering dense Ag deposition distinct from that observed in conventional titania-based nanomaterials and other ultrathin materials. The Ag nucleation is likely initiated at intrinsic Ti⁴⁺ vacancy sites distributed within the 2D structure, and the growth appears to be primarily governed by interfacial states. Specifically, annealing at 400 °C promotes the decomposition of tetra-n-butylammonium cations, possibly producing smaller ionic species, such as nitrogen-containing fragments and/or H₃O⁺ at the monolayer-substrate interface. These species could passivate Ti⁴⁺ vacancy sites, thereby suppressing Ag growth on monolayer titania NSs. Without annealing, larger C₄N⁺ species with lower charge density remain more abundant at the interface and could interact weakly with the active sites, allowing Ag PD to extend by several nanometers. This work provides a conceptual basis for defect-interface engineering of dense and tunable metal photodeposition on atomically thin semiconductor platforms.

Interfacial engineering is a widely adopted strategy for mitigating dendrite growth in solid-state lithium (Li) metal batteries (SSLMBs). This strategy typically involves depositing a thin-film interlayer on the solid electrolyte (SE) surface to enhance lithiophilicity, mechanical compliance, and uniform current distribution. However, whether the process of constructing a thin-film interlayer damages the SE remains unclear. If so, how can a systematic deposition protocol be established to construct a damage-free interlayer/SE interface? Here, we deposited W and Cu thin-film interlayers on the surface of the SE by magnetron sputtering and thermal evaporation, respectively, two commonly used techniques in interface engineering. Cryogenic focused ion beam (cryo-FIB) and transmission electron microscopy (TEM) analyses reveal that both processes can severely damage the near-surface crystal structure of the SE, inducing surface amorphization and forming an additional Li-containing compound layer at the interface. More importantly, we show that proper selection of deposition techniques and interlayer materials enables a damage-free interlayer/SE interface. In situ TEM observation reveals distinct Li deposition behaviors at damaged and damage-free interfaces, highlighting the importance of interfacial structural integrity in regulating Li deposition. This work reveals the interfacial damage mechanism during interlayer construction, providing important guidance for optimizing interfacial engineering toward long-cycle-life SSLMBs.

Atomic force microscopy (AFM) is a versatile multi-modal imaging method frequently used for structural characterisation of biological surfaces at the nanoscale. However, AFM-based three-dimensional single-particle reconstruction has hitherto not been possible due to the tip-sample convolution artifact that distorts AFM images of individual molecules, and the disconnect between two-dimensional AFM images of surface deposited molecules and their three-dimensional structures. Here, three-dimensional single-particle analysis was developed for rapid structure-based validation of protein structures using as few as a single AFM topology image, based on contact-point reconstruction AFM (CPR-AFM) in an integrative approach with cryo-electron microscopy maps available in the Electron Microscopy Data Bank by template matching. This approach was demonstrated on the structural validation of recombinant trimeric ectodomain of SARS-CoV-2 Spike glycoprotein to show its immediate utility for rapid structure-based quality-control in the recombinant expression and purification of Spike protein samples that can be used in vaccines and therapeutics research. These results show that three-dimensional single-particle reconstruction by AFM is possible, high signal-to-noise AFM imaging offers a rapid and cost-effective way of validation or identification of three-dimensional protein structures at single-particle level, and AFM linked to cryo-electron microscopy-derived structural data result in integrative methodologies with new capabilities for structural biology.

Understanding how structural modifications influence charge transport in DNA is central to biomolecular electronics. In this study, we investigate the effect of daunomycin intercalation on DNA stability and charge transport. We employ a combination of classical molecular dynamics simulations, electronic structure calculations, and charge transport within the Landauer-Büttiker framework. The intercalation significantly enhances DNA rigidity, with bis-daunomycin providing further stabilization due to the linker. The results show that the bis-daunomycin intercalation enhances conductance by nearly threefold, despite the presence of a non-conjugated linker. The conductance enhancement arises from the cooperative interplay of linker-induced structural stabilization and intercalator-derived electronic states, with structural stabilization providing the dominant differentiating factor. Additionally, intercalation introduces daunomycin-derived states near the LUMO region, leading to a reduction in the HOMO-LUMO gap from 4.22 eV to 2.23 eV. These findings highlight the importance of structural stabilization in tuning quantum transport properties and suggest the potential of bis-intercalators for DNA-based nanoelectronic applications.

Sodium-ion (Na-ion) batteries are moving from validation to deployment, yet durable full-cell operation is now limited by the chemistry, structure, and mechanics of nanoscale electrode-electrolyte interphases rather than by bulk-material discovery. The solid (SEI) and cathode (CEI) electrolyte interphases in Na-ion cells cannot be read as scaled lithium analogs. They are nanoscale, mosaic, dynamically reorganizing layers shaped by a Na⁺ solvation sheath, electrical double layer, and chemo-mechanical environment that differ markedly from Li⁺ analogs. This article reframes Na-ion interphase design around three linked ideas: (i) the primary Na⁺ solvation sheath, not the bulk electrolyte-stability window, selects first-layer chemistry at the nanoscale, through adsorption, desolvation and absorption at the electrode surface; (ii) under lean electrolyte and practical negative-to-positive (N/P) ratios, both interphases co-evolve through cross-talk rather than as independent passivation layers; and (iii) credible mechanistic claims require an explicit evidence-tier hierarchy and minimum reporting set. We anchor the discussion in deployment-relevant markers, including a representative hard-carbon full-cell ICE near 91.4%, a reported optimal N/P of about 0.9 in a layered-oxide/hard-carbon pairing, and emerging 1.5 and 3.5 A h cylindrical Na-ion formats, and close with a co-design logic and benchmarking checklist for Na-ion full-cell interphase studies.

Psoriasis is a chronic inflammatory skin disease, commonly managed using a combination of oral methotrexate (MTX) and injected TNF-α inhibitors. However, these often result in systemic side effects. Here, we report a gelatin methacryloyl-based (GelMA) hydrogel microneedle patch for the localized co-delivery of MTX and DNA tetrahedral-loaded TNF-α siRNA (MTX-TDN-siRNA MNs), integrating various administration methods into a unified transdermal platform. In an imiquimod (IMQ)-induced psoriasis mouse model, the MTX-TDN-siRNA MNs treatment demonstrated robust therapeutic efficacy, evidenced by improved PASI scores and epidermal normalization. The combined treatment strategy achieved enhanced outcomes compared to monotherapies of MTX or TNF-α siRNA. Moreover, the GelMA-based microneedles significantly reduced the MTX dosage, thereby minimizing systemic toxicity, as indicated by stable serum biochemical markers. This transdermal platform integrates chemotherapeutic and genetic agents, offering a safe, convenient, and efficient combinatory therapy for psoriasis.

Since its experimental realization in 2004, graphene has revolutionized materials science due to its extraordinary two-dimensional (2D) architecture and exceptional physicochemical properties. Graphene oxide (GO), a pivotal derivative of graphene, exhibits immense potential for multifunctional nanocomposites, attributed to its unique 2D framework, abundant surface functional groups, and excellent solution processability. This review establishes structural engineering as the foundational paradigm for designing graphene-based nanocomposites with integrated multifunctionality. We systematically examine how structural engineering governs multiscale architectures from atomic-level defect configurations to macroscopic assembly geometries and elucidate the underlying structure-property relationships through mechanistic frameworks including phonon transport theory, percolation theory, and composite micromechanics. In-depth analyses of multifunctional applications in mechanical engineering, electronics, energy storage, environmental remediation, and biomedicine are presented, with explicit attention to both demonstrated advantages and persistent limitations of each application category. Critically, we identify and analyze four key industrialization bottlenecks, including structural controllability, batch consistency, scale effects, and cost-effectiveness trade-offs that currently impede the transition from laboratory achievements to scalable manufacturing. By synthesizing existing research findings with industrialization considerations, this review offers a critical assessment of the field's current state and provides actionable theoretical guidance and technical pathways for the precise design and large-scale industrialization of graphene-based nanocomposites.