In lithium (Li) metal batteries, lithophilic materials play an essential role in stabilizing Li metal anodes. However, it is very difficult to attenuate the reactivity with Li while maintaining their lithophilicity. Herein, we propose a "lithophilic yet inert interfaces strategy" to stabilize Li metal anodes. That is, the chemically/mechanically stabilized composite BP@MOFs are formed by in situ growth of metal-organic frameworks (MOFs) on the surface of black phosphorus (BP), which can be used as an artificial interface to stabilize Li metal anodes. Among them, the highly conductive porous MOFs provide enriched channels for the migration of Li-ion (Li+). A series of experiments and theoretic analysis are utilized to reveal that charge transfer between BP and the metal ions reduces the electron density on the BP surface, thereby weakening its reactivity while maintaining its lithophilicity. It inhibits excess Li consumption and suppresses the excessive expansion of the BP volume in the continuous exfoliation/deposition process. Accordingly, the protected Li anodes can undergo reversible Li plating/stripping over 2000 h at a current density of 1 mA cm-2. Coupling the BP@MOF-Li with a sulfur cathode, the Li-S cell shows an excellent capacity retention of 88.1% after 500 cycles, with a fading rate of less than 0.024% per cycle.

Traditional petroleum distillation faces high energy demands, necessitating innovative alternatives like membrane separation. This study presents a breakthrough in dual-range and precise pore size modulation of metal-organic frameworks (MOFs) through a ligand functionalization strategy. By tailoring steric configurations and spatial orientations of light-responsive azobenzene groups, we achieved broad-range pore tuning (0.41 to 0.68 nanometers) via functional group length variation, coupled with subnanometer precision through reversible trans-to-cis photoisomerization. Four representative branched alkanes were selected to validate the MOF's high selectivity. Results showed its capacity to generate a constant carbon-atom-count-dependent permeation gradient, realizing a four-step sequential separation that increased C6H14 purity from 25 to 92.2%. This synergistic approach uniquely combines large-scale pore adjustment with dynamic fine-tuning, decoupling separation efficiency from energy-intensive processes. The membranes' structural stability and reversible light responsiveness further highlight their potential for sustainable hydrocarbon processing. By integrating molecular design with stimuli-responsive control, this work advances MOF-based membranes as a transformative solution for energy-efficient petroleum fractionation and precise molecular sieving.

Unravelling the mechanism of electronic state evolution is ultimately important when attempting to functionalize two dimensional (2D) materials through electronic state regulation. However, there is still a lack of understanding in how the individual local functionalized regions could influence the entire 2D-layered property. Herein, we report the observation of surface electronic behavior during these functionalization process when utilizing the electron-deficient aluminium ion (Al3+) to passivate 2D black phosphorus (BP). Interestingly, the local electron density change in response to a certain functionalization can induce the periodic electron density gradient via inductive integration effect and spread over the entire 2D surface layer. Such 2D coupling effect is evidently supported by the combined investigation of in-situ/ex-situ experimental analysis and theoretical calculation, upon the model Al3+-BP modulating process. This work discloses the electron-level relationship between the individual and the whole during the functionalization process and therefore provides a direction for precise manipulation of electronic behavior in functionalized 2D materials.

Hard carbon (HC) is considered the most promising anode material for commercial sodium-ion batteries (SIBs), yet it still faces critical challenges such as low initial Coulombic efficiency (ICE). Presodiation can improve ICE by compensating for sodium loss caused by irreversible defects in HC. However, research on how the active sodium content during presodiation affects the formation and stability of the preconstructed solid electrolyte interface (SEI) remains limited. Based on this background, this work introduces many pyrrolic nitrogen (N-5) sites into HC through pyrolysis of a urea-HC composite, working in synergy with chemical presodiation to enhance sodium-ion provision. Experimental and theoretical investigations reveal that the N-5 sites strengthen the adsorption capability for Na+ and its ability to capture PF6 - from the electrolyte, promoting the preformation of a stable, inorganic-rich SEI layer. As a result, the PS-0.5NHC achieves an excellent ICE of 98.54%, a capacity retention of 90.6% after 1000 cycles at 1.5 A g-1. In a full-cell configuration, the ICE is also significantly improved from 70.74% to 91.53%. This work provides a novel design concept for mitigating the inherent defects of the HC anode.

Precise regulation of interfacial ion transport while suppressing electrolyte-induced side reactions is a long-standing challenge for hard carbon (HC) anodes in sodium-ion batteries, where uncontrolled molecular access to the carbon surface leads to unstable solid-electrolyte interphases and rapid capacity fading. Here, we present a molecular steric-hindrance engineering strategy by covalently grafting aromatic molecules with systematically tuned substituents onto biomass-derived HC, enabling fine control over the surface nanospace to selectively permit Na+ transport while blocking organic electrolyte species. The optimally engineered interface promotes the formation of a uniform, inorganic-rich solid-electrolyte interphase, accelerates Na+ diffusion kinetics, and mitigates parasitic reactions. As a result, the modified HC delivers high initial Coulombic efficiency, large reversible capacity, excellent rate capability, and remarkable long-term stability in both half- and full-cells. This steric modulation concept provides a versatile and generalizable route for interfacial design, offering new opportunities for the development of high-performance carbon-based anodes in sodium-ion batteries.

Electronic effects of organic functional groups play a fundamental role in determining the rate and/or direction of organic chemical reactions. The implementation of this concept in selective organic catalysis is achieved by tuning the electronic effects of organic functional groups to alter the corresponding reactivity. However, this approach has hardly been applied to modulate the band structure of inorganic materials. Here, we show that modulating the electronic band structure of two-dimensional black phosphorus (BP) is possible via the electronic effects of organic functional groups covalently modified on its surface. Organic functional group can either donate or withdraw charge density from BP surface, which will alter the bonding/anti-binding orbitals occupancy and thus shift the band-edge positions of functionalized BP downward/upward. Therefore, the valence-band maxima and the conduction-band minima of functionalized BP can be continuously tuned by changing the binding group with different Hammett parameters. Finally, unexpectedly high hydrogen evolution reaction rates under visible light are achieved using functionalized BP heterojunctions as photocatalysts. This work underscores the significant role of electronic effects in chemically controlling BP's band structure, offering greater flexibility and affordability beyond physical method limits.

Surface-enhanced Raman scattering spectroscopy (SERS) can provide molecular fingerprint peaks of the vibration information with great specificity and sensitivity. It is widely used in biomedical and chemical fields. Semiconductor-based substrates represent a hot spot in the field of SERS beyond conventional noble metals, and metal-organic frameworks are rarely realized for SER detection. Here, we modulate the energy-band structures of metal-organic frameworks (MOFs) further by metal oxides (MOs) to match the energy band of a target analyte. We construct MOF-encapsulated metal oxide core-shell nanoparticles (MO@MOFs) as substrates for Raman enhancement. Attributed to the high structural tailorability of both core and shell, a series of energy-band structures have been created. We perform SERS detection of rhodamine b (RhB) on MO@MOF and find that the enhanced factor of Fe3O4@MOF(Co) and TiO2@MOF(Ni) reach as high as 10(8) and 10(6), respectively, with low detection limits of 10(-8) M, much lower than that using the corresponding MOFs. The SERS enhancement is based on mechanisms including charge transfer, interband and molecule resonances, and ground-state charge-transfer interactions. This work will promote the application of semiconductor-based nanomaterials with special modularity for surface-enhanced Raman scattering substrates.

MicroRNA (miRNA) is an important biomarker for early diagnosis of cancers. However, sensitive and convenient methods for miRNA detection remain a challenge. Here, we use a natural biopolymer sporopollenin purified from Ganoderma lucidum spores as a substrate for isothermal amplification (hybridization chain reaction, HCR). Sporopollenin capsules (SP) promotes HCR and forms longer and more abundant double-stranded DNA (dsDNA) than graphene oxide (GO) and carbon nanotubes (CNTs). The nanoporous structure of sporopollenin capsules containing abundant water provides a hydrous environment and enhances the hybridization efficiency of DNA significantly. We construct an ultrasensitive fluorescent biosensor to detect miR-155. The efficient HCR amplification on SP leads to an ultralow detection limit of 1 aM for miR-155 and a wide linear range of 1 aM-10 fM (R2 = 0.99). Furthermore, our fluorescence biosensor can discriminate miRNA mutants with high selectivity. This biosensor is also highly sensitive in human serum (detection limit 10 aM). It adsorbs less serum protein than GO and CNTs, thus minimizing the interference caused by the non-specific adsorption. Our study would promote medical application of SP-based biosensor in the future.

Exosomes, extracellular vesicles secreted by cells, play a crucial role in intercellular communication by transferring information from source cells to recipient cells. These vesicles carry important biomarkers, including nucleic acids and proteins, which provide valuable insights into the parent cells' status. As a result, exosomes have emerged as noninvasive indicators for the early diagnosis of cancer. Colorimetric biosensors have garnered significant attention due to their cost-effectiveness, simplicity, rapid response, and reproducibility. In this study, we employ sporopollenin microcapsules (SP), a natural biopolymer material derived from pollen, as a substrate for gold nanoparticles (AuNPs). By modifying the SP-Au complex with CD63 aptamers, we develop a label-free colorimetric biosensor for exosome detection. In the absence of exosomes, the SP-Au complex catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB), resulting in a color change from colorless to blue. However, the addition of exosomes inhibits the catalytic activity of the SP-Au complex due to coverage of exosomes on AuNPs. This colorimetric biosensor exhibits high sensitivity and selectivity for exosome detection, with a detection limit of 10 particles/μL and a wide linear range of 10 - 108 particles/μL. Additionally, the SP-Au biosensor demonstrates remarkable resistance to serum protein adsorption and excellent catalytic stability even in harsh environments, making it highly suitable for clinical diagnostics.

Circulating tumor DNA (ctDNA) is an auspicious tumor biomarker released into the bloodstream by tumor cells, offering abundant information concerning cancer genes. It plays a crucial role in the early diagnosis of cancer. However, due to extremely low levels in body fluids, achieving a simple, sensitive, and highly specific detection of ctDNA remains challenging. Here, we constructed a purification-free fluorescence biosensor based on quadratic amplification of ctDNA by combining nicking enzyme mediated amplification (NEMA) and catalytic hairpin assembly (CHA) reactions. After double isothermal amplification, this biosensor achieved an impressive signal amplification of nearly 107-fold, enabling it to detect ctDNA with ultra-sensitivity. And the detection limit of this biosensor is as low as 2 aM. In addition, we explored the influence of human serum on the performance of the biosensor and found that it showed favorable sensitivity in the presence of serum. This biosensor eliminates the need for an intermediate purification step, resulting in enhanced sensitivity and convenience. Thus, our purification-free fluorescent biosensor exhibits ultra-high sensitivity when compared to other biosensors and has the potential to serve as an effective diagnostic tool for early detection of cancer. A quadratic amplification fluorescence biosensor constructed by combining nicking enzyme mediated amplification (NEMA) and catalytic hairpin assembly (CHA) reactions. After quadratic amplification, this biosensor achieved nearly 107-fold, enabling it to detect ctDNA with ultra-sensitivity.

Immune cells are the housekeepers of the human body. They protect the body from pathogens, cellular damage, and foreign matter. Proper activation of immune cells is of great significance to diseases such as infection, inflammation, and neurodegeneration. However, excessive activation of cells can be detrimental. An ideal biomaterial could enhance the cellular immune function without proinflammation. In this work, we used sporopollenin exine capsules (SEC) from pollen to promote functions of primary microglia, a typical resident immune cell of the brain. We found that microglia aggregated around SEC and did not undergo any proinflammation. SEC improved the viability, migration, phagocytosis, and anti-inflammatory ability of microglia. By exploring the underlying mechanism of microglial activation without the production of cytotoxic pro-inflammatory cytokines, we found that SEC protects microglia against inflammation induced by lipopolysaccharide (LPS), an immunostimulatory factor, through the toll-like receptor 4 (TLR4) signaling pathway in a myeloid differentiation factor 88-dependent manner. These findings might shed light on the potential application of SEC in microglia transplantation for treatment of microglia-associated degenerative central nervous system diseases.

For many years, tool wear has been a critical issue with respect to productivity, cost, and part quality, particularly for superalloy machining. The underlying wear mechanisms of a new turning tool, FreeTurn, is revealed in this paper towards its potential for a more sustainable way of metal cutting. It is a specially designed turning tool that is held by the tool spindle and has a working plane perpendicular to the centreline of the tool spindle, making it rotatable on its working plane. Owing to the unique feature of FreeTurn compared with conventional turning tools, the focus of this study is on the effect of dynamic tool–workpiece engagement on tool wear. The tool path strategy is first set to achieve a cylindrical surface in longitudinal turning with a rotatable FreeTurn tool. Series of experiments with different tool path strategies are performed on a turn–milling machine, using Inconel 718 as an example of workpiece material. The results indicate that the coupling effect between notch and flank wear is the decisive factor of tool wear in free turning with respect to its rotation and feeding directions. While the tool wear can be significantly reduced if the tool feeds with increasing cutting edge angle, the tool will soon be worn out if it feeds with decreasing cutting edge angle. Tool rotation in free turning plays a key role in reducing adhesion on the cutting tool and increasing the tool rotation speed can further improve this effect. Additionally, a more sustainable solution that uses both sides of the cutting edge becomes possible with FreeTurn as well, improving the tool utilisation. The results demonstrate considerable guiding significance for exploring the potential of this new turning tool towards a longer tool life.

Chemotherapy is commonly used for the treatment of lung cancer, but strong side effects and low treatment efficacy limit its clinical application. Here, extracellular vesicles (EVs) as natural drug delivery carriers were used to load conventional anticancer drug doxorubicin (DOX) and a chemosensitizer lonidamine (LND). Two types of EVs with different sizes (16k EVs and 120k EVs) were prepared using different centrifugation forces. We found that co-delivery of DOX and LND with both EVs enhanced the cytotoxicity and reduced the dose of the anticancer drug significantly in vitro. Effective delivery of anti-cancer drugs to cancer cells was achieved by direct fusion of EVs with the plasma membrane of cancer cells. On the other hand, DOX and LND inhibited cancer cell proliferation by increasing DNA damage, suppressing ATP production, and accelerating ROS generation synergistically. DOX and LND loaded EVs were also applied to the mouse lung cancer model and exhibited significant anticancer activity. In vivo study showed that smaller EVs exhibited higher anticancer efficiency. In conclusion, the co-delivery of the anticancer drug and the chemosensitizer with EVs may have potential clinical applications for cancer therapy.

Holey amorphous FeCoO-coated black phosphorus serves as an ideal sulfur host with great structural and compositional features to alleviate the shuttling effect and consequently enhance the performance of lithium–sulfur batteries.

Background and Aims : Endothelial inflammation and dysfunction contribute significantly to atherosclerosis. Rutaecarpine, isolated from Chinese medicinal herb-Tetradium ruticarpum, is a bioactive alkaloid with anti-atherosclerotic effects via suppressing macrophage-derived foam cell formation. However, the pharmacological effects and molechanism whereby rutaecarpine protects against endothelial dysfunction remain unknown. Given inflammation is a significant contributor to endothelial dysfunction and atherosclerosis, the present study was designed to examine the pharmacological effects of rutaecarpine in regulating endothelial inflammation and the mechanism of action involved.Methods: HUVE cells were pre-incubated with rutaecarpine (5, 10μM) overnight and then treated with TNFα(10ng/ml) for 6hours. Cell viability, endothelial inflammation,monocyte adhesion and NF-κB pathway were investigated by CCK-8 assays, wb, qPCR and luciferase assays.Results: We found rutaecarpine did not have endothelial toxicity ranging from 1 to 10μM. Rutaecarpine significantly alleviated endothelial inflammation induced by TNFα, with decreased ICAM1,VCAM1 and E-selectin expression. Of relevance, the anti-inflammatory effects of rutaecarpine lead to ameliorated monocyte adhesion to TNFα-activated endothelium. Mechanistically, rutaecarpine downregulated the transcriptional activity of NF-κB, without influencing the activation of the upstream MAPK (p38,JNK,ERK) signaling pathway and nuclear translocation of NF-κB. To gain a comprehensive understanding of endothelial protective effects of rutaecarpine, we performed a transcriptomic profing study in rutaecarpine-treated endothelial cells in the presence of TNFα. Our RNA-seq and integrated bioinformatic analysis revealed rutaecarpine suppressed inflammatory pathways as well as activated the Nrf2 pathway.Conclusions: Rutaecarpine ameliorates endothelial inflammation by inhibition of NF-κB and activation of Nrf2. Our findings suggest the therapeutic potential of anti-inflammatory alkaloid compounds from herbal medicine against endothelial dysfunction and associated. Background and Aims : Endothelial inflammation and dysfunction contribute significantly to atherosclerosis. Rutaecarpine, isolated from Chinese medicinal herb-Tetradium ruticarpum, is a bioactive alkaloid with anti-atherosclerotic effects via suppressing macrophage-derived foam cell formation. However, the pharmacological effects and molechanism whereby rutaecarpine protects against endothelial dysfunction remain unknown. Given inflammation is a significant contributor to endothelial dysfunction and atherosclerosis, the present study was designed to examine the pharmacological effects of rutaecarpine in regulating endothelial inflammation and the mechanism of action involved. Methods: HUVE cells were pre-incubated with rutaecarpine (5, 10μM) overnight and then treated with TNFα(10ng/ml) for 6hours. Cell viability, endothelial inflammation,monocyte adhesion and NF-κB pathway were investigated by CCK-8 assays, wb, qPCR and luciferase assays. Results: We found rutaecarpine did not have endothelial toxicity ranging from 1 to 10μM. Rutaecarpine significantly alleviated endothelial inflammation induced by TNFα, with decreased ICAM1,VCAM1 and E-selectin expression. Of relevance, the anti-inflammatory effects of rutaecarpine lead to ameliorated monocyte adhesion to TNFα-activated endothelium. Mechanistically, rutaecarpine downregulated the transcriptional activity of NF-κB, without influencing the activation of the upstream MAPK (p38,JNK,ERK) signaling pathway and nuclear translocation of NF-κB. To gain a comprehensive understanding of endothelial protective effects of rutaecarpine, we performed a transcriptomic profing study in rutaecarpine-treated endothelial cells in the presence of TNFα. Our RNA-seq and integrated bioinformatic analysis revealed rutaecarpine suppressed inflammatory pathways as well as activated the Nrf2 pathway. Conclusions: Rutaecarpine ameliorates endothelial inflammation by inhibition of NF-κB and activation of Nrf2. Our findings suggest the therapeutic potential of anti-inflammatory alkaloid compounds from herbal medicine against endothelial dysfunction and associated.

Background and Aims : Preclinical mouse models are lacked in predicting the pathomechanisms of cardiometabolic diseases and explore new therapeutic agents. Using double-knockouts in ApoE−/− or LDLR−/− background mice are impractical due to the extensive amount of breeding required and substantial costly. Recently reports indicated that overexpression of PCSK9 (AAV8-PCSK9) can induced spontaneous hyperlipidemia which mediated by adeno-associated-virus-8 (AAV8). The purpose of our research was to assess the injection of AAV-PCSK9 vectors in db/db mice as a novel compound mouse model of diabetes, atherosclerosis and fatty liver to study the cardiometabolic diseases and complications.

The formation and growth of Li-dendrites caused by inhomogeneous Li deposition severely hinder the commercial applications of Li metal batteries due to the consequence of short-circuiting. Herein, we pro-pose a Janus bilayer composed of black phosphorus (BP) and graphene oxide (GO) as an artificial interface with chemical/mechanical stability and well-regulated Li-ion flux distribution for Li metal anode protec-tion. Owing to the synergy between the fast Li-ion transport of BP in the inner layer and the high mechan-ical and chemical stability of GO in the outer layer, the GO/BP with good electrolyte wettability acts as a Li-ion regulator that can induce homogeneous growth of Li to suppress the Li dendrites growth. Accordingly, long-term stability (500 h at 1 mA cm?2) with a low overpotential of 30 mV is achieved in the symmetric cell with GO/BP-Li anode. Furthermore, the Li-S cell with GO/BP-Li exhibits enhanced cycling performance with a high capacity retention rate of 76.2 % over 500 cycles at 1 C.(c) 2022 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

The two-dimensional black phosphorus can interact with metal compounds to form BP–M composites, showing tailored properties. This review summarizes BP–Ms in different applications, revealing the challenges and prospects of this composite material.

Transition metal carbides/nitrides (MXenes) are a newly developing class of two-dimensional (2D) materials with technically robust properties that can be finely tuned by planar surface functionalization. Herein, the critical role of oxygen (O-) functionalization on the tensile mechanical characteristics of thinnest 2D Ti2C MXene is explored by molecular dynamic (MD) simulation with first-principle based ReaxFF forcefield. It is demonstrated that Ti2C sheet shows unique tensile mechanical behaviors that pronouncedly vary with the content of O-functionalization and stretching direction. Upon both loading directions, there is an apparent crossover in the Young's modulus, failure strength and failure strain. Intriguingly, under armchair directional load, a structural transition of 1T to 1T' phase occurs in the Ti2C region, which has been observed in many transition metal dichalcogenides. Upon zigzag directional straining, however, two distinct structural transformations take place in pristine and fully O-functionalized Ti2C sheets, respectively. As the load is removed, those three structural transformations are reversible, and they are critically understood by analysis of the bond configurations. The study provides important insights into mechanical behaviors and structural transformations of functionalized MXenes.