Nanoscale Horizons最新文献

The global crisis of multidrug-resistant bacterial infections, coupled with the cytotoxicity of conventional metal-based therapeutics, necessitates the development of highly biocompatible antimicrobial agents. In this work, we have developed gallium (Ga)-based nanoparticles integrated with EGCG (Ga-EGCG NPs), which demonstrated potent antibacterial activity with excellent biocompatibility in both in ovo (chick chorioallantoic membrane) and in vitro (MTT and hemolysis) assays. Comprehensive characterisation using UV-vis, FT-IR, TEM and XPS confirmed the successful synthesis of spherical Ga-EGCG NPs. Consistent with gallium's 'Trojan horse' mechanism exploiting bacterial iron-uptake pathways, antibacterial efficacy depended strongly on iron availability. Under iron-limited conditions, Ga-EGCG NPs demonstrated significant potency, with MIC values of 5 µg mL^-1 against Bacillus subtilis, 50 µg mL^-1 against Escherichia coli 739, 100 µg mL^-1 against Escherichia coli 443, 100 µg mL^-1 against Pseudomonas aeruginosa and 250 µg mL^-1 against methicillin-resistant Staphylococcus aureus (MRSA). Conversely, significantly higher MICs in iron-rich media highlighted the critical role of iron competition. Beyond growth inhibition, Ga-EGCG NPs effectively inhibited biofilms and induced reactive oxygen species (ROS) generation, as confirmed by DCFH-DA assays. SEM imaging and live/dead staining further revealed compromised bacterial cell membranes upon treatment with NPs. Additionally, Ga-EGCG NPs displayed strong antioxidant activity in DPPH and ABTS assays. Importantly, Ga-EGCG NPs exhibited no observable toxicity in the in ovo model, minimal hemolysis (<10%) even at 250-fold MIC, and negligible cytotoxicity toward L6 and 3T3-L1 cell lines, highlighting their superior biocompatibility. Overall, these findings establish Ga-EGCG NPs as a highly biocompatible, iron-dependent antibacterial agent and as a safer alternative to existing antimicrobial strategies.

Driven by the imperative for scalable energy storage and the global carbon neutrality initiatives, coal-derived hard carbon has garnered significant attention as a cost-effective and highly tunable anode material for sodium-ion batteries. This review systematically explores the inherent structure-property relationships of coal-based hard carbon, tracking its microstructural evolution across different coal ranks and molecular architectures. We critically examine the prevailing debates on sodium-storage mechanisms, particularly evaluating the respective contributions of adsorption, interlayer intercalation, and nanopore filling models. To address the persistent challenges of low initial coulombic efficiency (ICE) and limited plateau capacity, a comprehensive summary of advanced microstructural modulation strategies is provided. These cutting-edge approaches include precursor pretreatment, pore-structure engineering, template-confined carbonization, and soft-hard carbon composite construction. Current research underscores that precisely enlarging the graphitic interlayer spacing, constructing well-defined closed-pore networks, and suppressing excessive graphitization are paramount for synergistically boosting both specific capacity and ICE. Finally, this review outlines critical future perspectives, emphasizing the integration of in situ characterization, multiscale simulations, and low-cost scalable manufacturing pathways to accelerate the commercialization of coal-based sodium-ion batteries.

The development of lithium metal batteries (LMBs) has been hindered by the high cost and environmental issues associated with conventional fluorinated electrolytes, and regulatory concerns over perfluoro- and polyfluoroalkyl substances (PFAS) have accelerated the shift toward non-fluorine electrolyte systems as a sustainable alternative. As a result, chloride-functionalized electrolytes, taking advantage of the unique properties of chlorine atoms, have emerged as a promising alternative solution, featuring inherent flame retardancy, improved high-voltage stability and the formation of a LiF/LiCl hybrid interface conducive to kinetics. In this minireview, we systematically reviewed this paradigm shift, analyzing the molecular design, solvation structure regulation and interfacial engineering of chlorinated systems. We highlight their exceptional performance in high voltage, wide-temperature ranges, and long cycle operations, along with their evolution from functional additives to core electrolyte components. Our primary objectives are to provide a comprehensive and critical analysis of the structure-property relationships, performance advantages, and existing challenges in this field. This minireview aims to establish a foundational framework and identify future research directions for developing chlorinated electrolytes, ultimately guiding the design of safer and more sustainable LMBs.

Mesoporous polydopamine (MPDA) nanocarriers exhibit significant advantages in tumor drug delivery and immunotherapy owing to their well-defined mesoporous structure, modifiable surface chemistry, environmentally responsive degradation, and efficient photothermal properties. MPDA nanoparticles possess a high specific surface area and tunable pore channels, enabling efficient loading and controlled release of various therapeutic molecules. The abundant catechol and amine groups on their surface facilitate convenient functionalization, which is beneficial for targeted modification. The photothermal effect triggered by near-infrared laser irradiation not only enables localized tumor ablation but also induces immunogenic cell death, thereby activating antitumor immune responses. The acid-responsive degradation behavior of MPDA in the tumor microenvironment allows controlled drug release, while its degradation products can further promote macrophage phenotype reprogramming, thereby improving the immune microenvironment. By loading immune checkpoint inhibitors, immune adjuvants, and metabolic regulatory molecules, MPDA-based nanosystems can effectively alleviate tumor-induced immunosuppression and enhance immunotherapy responses. Additionally, this platform can optimize lymphatic transport efficiency, promote nanoparticle accumulation in draining lymph nodes, and subsequently facilitate dendritic cell maturation and effector T-cell activation. Although previous reviews have summarized the preparation methods and biomedical applications of MPDA-based nanoplatforms, a systematic review of their roles in modulating the tumor immune microenvironment and enhancing antitumor immune responses remains limited. Therefore, this review summarizes the latest advances in MPDA-based nanodrug delivery systems for cancer immunotherapy, with a particular focus on their immunomodulatory mechanisms and applications in multimodal synergistic cancer immunotherapy, aiming to provide insights into future development and clinical translation of MPDA nanotherapeutic systems.

Aqueous washing is necessary for high-nickel layered positive electrodes, yet the medium that removes residual LiOH and Li₂CO₃ also draws lithium from the lattice and converts the near-surface layered phase into an inactive rock-salt structure. Whether this conversion protects or harms the positive electrode is settled within a few nanometers, since a thin layer shields the surface while an overgrown one blocks lithium transport. We propose a chemical-equilibrium description of washing in which the activity of dissolved lithium sets the position of the interfacial Li⁺/H⁺ exchange, and the binding of water into Li⁺ hydration shells lowers the activity of free water available for proton transfer, together governing the thickness of the reconstructed layer. In LiNi_0.90Co_0.05Mn_0.05O₂, a lithium-rich medium displaces this equilibrium toward the reactant side and suppresses lattice lithium extraction without compromising residual lithium removal, an outcome inaccessible to a concentration-gradient description. This control holds the reconstructed layer within the protective range, whereas water washing drives it beyond and accelerates capacity fade. The lithium-rich medium yields a positive electrode that cycles above the pristine reference in graphite full cells, rendering the reconstructed surface phase a tunable variable rather than an inevitable degradation product.

Hydrogen peroxide (H₂O₂) is a widely used environmentally benign bulk chemical. Electrocatalytic synthesis via the two-electron oxygen reduction reaction (2eORR) has emerged as a core green alternative to the traditional anthraquinone process, which suffers from high energy consumption, heavy pollution, and significant storage/transportation safety risks. Microporous carbon-based materials are recognized as the most industrially promising electrocatalysts for the 2eORR. However, most existing studies focus on modulating intrinsic catalytic activity through oxygen functional groups (OGs), while the strong coupling between OGs and mass transport in microporous systems is largely overlooked. The intrinsic structure-performance relationship among OGs, microporous structure, mass transport behavior, and catalytic performance remains incompletely elucidated, representing a critical bottleneck for optimizing microporous carbon-based catalysts. Herein, using commercial microporous activated carbon as the substrate, we achieved precise and controllable modulation of the type and content of surface OGs via liquid-phase H₂O₂ oxidation and high-temperature annealing, while preserving the pristine carbon matrix's microporous framework. Combining systematic characterizations, electrochemical measurements, DFT calculations, and EIS analysis, we comprehensively elucidated the OG-mediated reaction-mass transport coupling mechanism within micropores. Our results show that the synergistic effect between OGs and micropores has a negligible impact on intrinsic 2eORR activity. In contrast, the steric hindrance of OGs (especially carboxyl groups) significantly compresses the effective micropore size and markedly increases reaction mass transport resistance, which is identified as the dominant cause of performance degradation. A clear positive trend correlation exists between OC-O group content and both mass transport impedance and rotational speed sensitivity. On this basis, we propose "rotational speed sensitivity" as a novel electrochemical metric for quantitatively characterizing intrinsic mass transport resistance. This study provides theoretical guidance and a new methodology for the rational design of high-performance carbon-based catalysts for efficient H₂O₂ electrosynthesis.

Suboptimal reactive oxygen species (ROS) production in photodynamic therapy (PDT) and chemodynamic therapy (CDT) due to tumor antioxidants and H₂O₂ constraints poses a challenge to their therapeutic efficacy. To address this, our study introduces GOx@MPN@Gel, a novel PDT/CDT platform that integrates glucose oxidase (GOx), luteolin, iron ions, a traditional Chinese medicine-inspired metal-phenolic network (MPN), and hydrogel (Gel) carriers to enhance ROS generation. Experimental results demonstrate GOx@MPN@Gel enhanced acid sensitivity, robust GOx activity, and significant ROS production. Both in vitro and in vivo tests validate its therapeutic potential. Within the tumor microenvironment, GOx@MPN@Gel effectively elevates H₂O₂ levels for CDT, producing cytotoxic hydroxyl radicals (˙OH), and upon near infrared (NIR) light exposure, its porphyrin component triggers potent PDT effects, generating additional ROS. This synergistic approach significantly enhances antitumor efficacy. The platform's unique design, combining acid-responsive degradation and PDT/CDT synergy, offers a promising personalized treatment strategy for breast cancer.

Rheumatoid arthritis (RA) is a chronic autoimmune disease characterized by destructive and symmetrical joint lesions and joint synovitis, with the main clinical manifestations including joint deformity, morning stiffness, and inflammation in the joints of the hands, feet, wrists and ankles, and the temporomandibular joints. Sinomenine is a natural alkaloid with anti-inflammatory, analgesic, immunosuppressive and bone-protective effects, showing great potential in the treatment of rheumatoid arthritis. However, sinomenine suffers from drawbacks such as poor water solubility, low bioavailability and rapid degradation, which compromise its therapeutic efficacy. Tetrahedral framework nucleic acid (TFNA) is a DNA nanostructure with excellent delivery capacity for small-molecule drugs. It can bind small molecules from traditional Chinese medicine through electrostatic interactions and groove binding, thereby improving bioavailability. In this study, using TFNA as a carrier, we constructed a drug delivery system with favorable stability and biocompatibility - the TFNA-SIN complex - to deliver SIN into synovial fibroblasts, exerting anti-inflammatory effects and inhibiting cell proliferation. TFNA-SIN inhibits the expression of M1 macrophages, promotes the expression of M2 macrophages, and suppresses inflammatory cell infiltration by blocking the NF-κB and extracellular regulated protein kinase (ERK) signaling pathways. Therefore, TFNA improves the bioavailability of SIN and reduces SIN-induced toxicity, representing a promising alternative agent for the treatment of RA.

The anomalous Hall effect (AHE) has emerged as a powerful probe of the interplay between magnetism, electronic band topology, and spin-dependent quantum transport in two-dimensional (2D) magnetic materials. While extensive efforts have been devoted to the AHE in 2D magnets, most studies have been confined to ultra-low temperatures or regimes far below room temperature, limiting both fundamental understanding and practical applicability. The recent discovery of several high-temperature van der Waals (vdW) ferromagnets has opened up a promising platform for investigating the underlying mechanisms and device opportunities of the AHE at and above room temperature. In this review, we provide a comprehensive overview of recent advancements of the AHE in room-temperature 2D vdW ferromagnets. We first summarize the macroscopic manifestations of the AHE in representative vdW ferromagnets operating at room temperature. Then, we provide an overview of typical vdW ferromagnetic systems exhibiting room-temperature AHE, with a particular focus on thickness dependence, Curie temperature, magnetic anisotropy, and materials engineering strategies such as chemical doping, strain engineering, and interface design, together with state-of-the-art synthesis techniques. Subsequently, we discuss and compare the key microscopic mechanisms underlying the AHE in these materials, including intrinsic Berry-curvature-driven contributions and extrinsic contributions. Based on this understanding, recent progress in electrically tuning the AHE via external electric fields and applied currents is systematically reviewed, highlighting their impacts on anomalous Hall resistance, coercivity, and critical temperature. We further summarize advances in different types of electrically controlled vdW magnetic prototype devices, including current-tunable AHE devices and magnetic tunnel junctions. Finally, we outline the significant progress achieved so far, identify the key remaining challenges, and propose promising directions for future research toward robust and functional room-temperature AHE.