ASAP (As Soon As Publishable)

The tailoring of spin-crossover films has made significant progress over the past decade, mostly motivated by the prospect in technological applications. In contrast to spin-crossover complexes in solution, the investigation of the ultrafast switching in spin-crossover films has remained scarce. Combining the progress in molecule synthesis and film growth with the opportunities at X-ray free-electron lasers, we study the photoinduced spin-state switching dynamics of a molecular film at room temperature. The subpicosecond switching from the S = 0 low-spin ground state to the S = 2 high-spin state is monitored by analyzing the transient evolution of the Fe L₃ X-ray absorption edge fine structure, i.e. element-specifically at the switching center of the Fe(II) complex. Our measurements show the involvement of an intermediate state in the switching. At large excitation fluences, the fraction of high-spin molecules saturates at ≈50%, which is likely due to molecule–molecule interaction within the film.

Even though the enhanced permeability and retention (EPR) effect is applicable for the passive targeting of solid tumors, many nanodrugs have failed to achieve meaningful clinical outcomes due to the heterogeneity of EPR effect. Therefore, understanding the mechanism of the EPR effect is crucial to overcome the obstacles nanomedicines face in clinical translation. The aim of this study was to establish a reliable method to increase awareness of the critical influencing factors of nanoparticle (NP) transport into tumors based on the EPR effect using a combined radiogenomics and clinical magnetic resonance imaging (MRI) technique and gene set pathway enrichment analysis. Employing poly(lactic-co-glycolic acid) (PLGA)-coated Fe₃O₄ NPs as the contrast agent, the monolayer and multilayer distribution of the NPs were observed and quantitatively analyzed by MRI, improving the accuracy of evaluating vascular permeability by MRI. By performing Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analyses of genes and pathways, we identified a variety of genes affecting vascular permeability, such as Cldn1, Dlg2, Bves, Prkag3, Cldn10, and Cldn8, which are related to tight junctions and control the permeability of blood vessels in tumors. The method presented here provides an MRI-supported approach to increase the breadth of data collected from genetic screens, reveals genetic evidence of the presence of NPs in tumors and lays a foundation for clinical patient stratification and personalized treatment.

Main conventional antithrombotic therapies often suffer from unsatisfactory treatment outcomes and the risk of undesirable tissue hemorrhage. Deep clot penetration, on-demand drug activation, and release within the clots remain significant challenges. While past efforts to develop nanomedicines and prodrugs have improved safety at the expense of therapeutic effects. Herein, we develop a self-piercing and self-activating nanoassembly composed of an oxidation-sensitive prodrug (TGL-S-Fmoc, TSF) of ticagrelor (TGL) and IR808 (a photothermal/photodynamic dual-effect photosensitizer). TSF readily coassembles with IR808 into a carrier-free hybrid nanomedicine. Upon laser irradiation, IR808 enables photothermal thrombolysis and deep clot penetration of TSF while also synergistically facilitating prodrug activation triggered by IR808-generated singlet oxygen (¹O₂) and the endogenous hydrogen peroxide within the clots. Following fibrin-targeting modification, the nanoassembly achieves self-indicating thrombus-targeted accumulation, self-piercing deep clot penetration, dual-priming prodrug activation, and inside-out thrombus ablation with favorable safety in vivo. This study advances the clinical translation of antithrombotic prodrugs and nanomedicines.

Chemoresistance remains a long-standing challenge after cancer treatment. Over the last two decades, RNA interference (RNAi) has emerged as a gene therapy modality to sensitize cancer cells to chemotherapy. However, the use of RNAi, specifically small-interfering RNA (siRNA), is hindered by biological barriers that limit its intracellular delivery. Nanoparticles can overcome these barriers by protecting siRNA in physiological environments and facilitating its delivery to cancer cells. In this review, we discuss the development of nanomaterials for siRNA delivery in cancer therapy, current challenges, and future perspectives for their implementation to overcome cancer chemoresistance.

Promoting tumor cell apoptosis through the catalytic regulation of reactive oxygen species (ROS) is an ideal therapeutic option for cancer. However, a stable and controllable exogenous source of ROS is still lacking. Efficient and controllable electrocatalysis has shown tremendous potential for cancer treatment, but its key challenge lies in achieving precise, efficient, and controllable electrocatalytic ROS production at the tumor site. This study describes an electrocatalytic treatment technique for hepatocellular carcinoma (HCC) based on traditional Chinese acupuncture. By attaching a biocompatible electrocatalyst NiO-P₇₀₀ with optimal atomic spacing to the surface of silver acupuncture needles, a high-concentration ROS microenvironment was generated around tumor cells via ORRs when the needles were electrified. This induction led to the accumulation of inflammatory factors (IL-1β, IL-6, and TNF-α) and macrophage infiltration, accelerating tumor cell apoptosis and necrosis. Both in vitro and in vivo experiments demonstrated that the rate of ROS production can be rapidly controlled by adjusting voltage and current. Importantly, the high concentration of ROS can be safely and effectively confined to the lesion site without affecting the entire body. Our study attempted to integrate electrocatalysis and acupuncture in HCC treatment, successfully regulating NiO-P atomic spacing and enhancing ORR performance, thereby presenting a safe and reliable perspective for HCC therapy.

The high-entropy concept affords an effective method to design and construct customized materials with desired characteristics for specific applications. Extending this concept to metal oxides, high-entropy oxides (HEOs) can be fabricated, and the synergistic elemental interactions result in the four core effects, i.e., the high-entropy effect, sluggish-diffusion effect, severe-lattice-distortion effect, and cocktail effect. All these effects greatly enhance the functionalities of this vast material family, surpassing conventional low- and medium-entropy metal oxides. For instance, the high phase stability, excellent electrochemical performance, and fast ionic conductivity make HEOs one of the hot next-generation candidate materials for electrochemical energy conversion and storage devices. Significantly, the extraordinary mechanical, electrical, optical, thermal, and magnetic properties of HEOs are very attractive for applications beyond catalysts and batteries, such as electronic devices, optic equipment, and thermal barrier coatings. This review will overview the entropy-stabilized composition and structure of HEOs, followed by a comprehensive introduction to the electrical, optical, thermal, and magnetic properties. Then, several typical applications, i.e., transistor, memristor, artificial synapse, transparent glass, photodetector, light absorber and emitter, thermal barrier coating, and cooling pigment, are synoptically presented to show the broad application prospect of HEOs. Lastly, the intelligence-guided design and high-throughput screening of HEOs are briefly introduced to point out future development trends, which will become powerful tools to realize the customized design and synthesis of HEOs with optimal composition, structure, and performance for specific applications.

In contrast to homogeneous enzyme catalysis, nanozymes are nanosized heterogeneous catalysts that perform reactions on a rigid surface. This fundamental difference between enzymes and nanozymes is often overlooked in kinetic studies and practical applications. In this article, using 14 nanozymes of various compositions (core@shell, metal–organic frameworks, metal, and metal oxide nanoparticles), we systematically demonstrate that nontypical features of nanozymes, such as multiple catalytic activities, chemical transformations, and aggregation, need to be considered in nanozyme catalysis. Ignoring these features results in the inaccurate quantification of catalytic activity. Neglecting the multiple activities led to a six-time underestimation of Mn₂O₃ oxidation activity and mischaracterization of this material as a low-active peroxidase-mimicking nanozyme. Additionally, overlooking chemical stability during catalytic reactions led to the reporting of high peroxidase-mimicking activity for Au@Ag nanoparticles, which, in reality, exhibited no intrinsic activity and oxidized the substrate through the leakage of Ag⁺ ions. Ignoring the chemical stability of Au@Prussian Blue nanoparticles may lead to more than four times overestimation of peroxidase-mimicking activity after just 24 h of storage. Finally, disregarding the colloidal stability of nanozymes led to a five-time inaccuracy in catalytic activity. These findings underscore the necessity of optimizing procedures to account for these factors in nanozyme kinetic measurements, which will in turn ensure more reliable biosensors and the success of other practical applications.

The ever-increasing volume of complex data poses significant challenges to conventional sequential global processing methods, highlighting their inherent limitations. This computational burden has catalyzed interest in neuromorphic computing, particularly within artificial neural networks (ANNs). In pursuit of advancing neuromorphic hardware, researchers are focusing on developing computation strategies and constructing high-density crossbar arrays utilizing history-dependent, multistate nonvolatile memories tailored for multiply–accumulate (MAC) operations. However, the real-time collection and processing of massive, dynamic data sets require an innovative computational paradigm akin to that of the human brain. Spiking neural networks (SNNs), representing the third generation of ANNs, are emerging as a promising solution for real-time spatiotemporal information processing due to their event-based spatiotemporal capabilities. The ideal hardware supporting SNN operations comprises artificial neurons, artificial synapses, and their integrated arrays. Currently, the structural complexity of SNNs and spike-based methodologies requires hardware components with biomimetic behaviors that are distinct from those of conventional memristors used in deep neural networks. These distinctive characteristics required for neuron and synapses devices pose significant challenges. Developing effective building blocks for SNNs, therefore, necessitates leveraging the intrinsic properties of the materials constituting each unit and overcoming the integration barriers. This review focuses on the progress toward memristor-based spiking neural network neuromorphic hardware, emphasizing the role of individual components such as memristor-based neurons, synapses, and array integration along with relevant biological insights. We aim to provide valuable perspectives to researchers working on the next generation of brain-like computing systems based on these foundational elements.

To achieve high accuracy and effectiveness in sensing and modulating neural activity, efficient charge-transfer biointerfaces and a high spatiotemporal resolution are required. Ultrathin bioelectrode arrays exhibiting mechanical compliance with biological tissues offer such biointerfaces. However, their thinness often leads to a lack of mechano-electrical stability or sufficiently high electrochemical capacitance, thus deteriorating their overall performance. Here, we report ultrathin (∼115 nm) bioelectrode arrays that simultaneously enable ultraconformability, mechano-electrical stability and high electrochemical performance. These arrays show high opto-electrical conductivity (2060 S cm^–1@88% transparency), mechanical stretchability (110% strain), and excellent electrochemical properties (24.5 mC cm^–2 charge storage capacity and 3.5 times lower interfacial impedance than commercial electrodes). The improved mechano-electrical and electrochemical performance is attributed to the synergistic interactions within the poly(3,4-ethylenedioxythiophene) sulfonate (PEDOT:PSS)/graphene oxide (GO) interpenetrating network (PGIN), where π–π and hydrogen bonding interactions improve conductive pathways between PEDOT chains and enhance the charge-transfer mobility. This ultrathin bioelectrode is compatible with photolithography processing and provides spatiotemporally precise signal mapping capabilities for sensing and modulating neuromuscular activity. By capturing weak multichannel facial electromyography signals and applying machine learning algorithms, we achieve high accuracy in silent speech recognition. Moreover, the high transparency of the bioelectrode allows simultaneous recording of electroencephalography (EEG) and functional near-infrared spectroscopy (fNIRS) signals, facilitating dual-mode brain activity analysis with both high temporal and high spatial resolution.

Aberrant energy and substance metabolic pathways of tumor cells critically support tumor cell proliferation by hijacking the resources from nonmalignant cells, thereby establishing a metabolite flow favorable to tumor progression. This metabolic adaptation of tumor cells further modulates the immune landscape, ultimately creating a tumor microenvironment characterized by drug resistance and immunosuppression. The synergistic regulation of energy and substance metabolic pathways might be a good antitumor therapeutic paradigm. However, due to the metabolic convergence, it is crucial to selectively modulate the aberrant metabolism of tumor cells without compromising the functionality of other cells. Small-molecule drugs have the ability to target a wide range of biomolecules for antitumor therapy, but their application is limited by undesirable toxicities. Constructing nanodrug delivery systems can improve their properties and allow for the inclusion of multiple drugs, thereby exerting synergistic antitumor effects. In this study, we developed a two-drug codelivery system using drugs-conjugated multibranched polymers to modulate tumor cell metabolism by exploiting synthetic lethal pathways for safe and effective antitumor therapy. By delivery of adapalene and erastin simultaneously through nanoparticles, the material and energy metabolism of tumor cells can be regulated. This nanoparticle construction achieves tumor tissue targeting and responsive drug release, alters metabolite flow within tumor cells, and effectively kills tumor cells. Additionally, the nanoparticles can reverse the tumor immunosuppressive microenvironment, starting from single-cell regulation to whole-lesion control.

Anionic redox has emerged as a transformative paradigm for high-energy layered transition-metal (TM) oxide cathodes, but it is usually accompanied by the formation of anionic redox-mediated oxygen vacancies (OVs) due to irreversible oxygen release. Additionally, external factor-induced OVs (defined as intrinsic OVs) also play a pivotal role in the physicochemical properties of layered TM oxides. However, an in-depth understanding of the interplay between intrinsic and anionic redox-mediated OVs and the corresponding regulation mechanism of the dynamic evolution of OVs is still missing. Herein, we disclose the strong interrelationship between these OVs and demonstrate that the presence of intrinsic OVs in the TMO₂ layers could induce weak integrity of the TM-O frameworks and unlock additional diffusion paths to trigger the generation and migration of anionic redox-mediated OVs. Accordingly, an OV stabilization strategy is proposed by deliberately introducing high-valence Nb⁵⁺, which could serve as an important building block in anchoring the oxygen sublattice and preventing the formation of a percolating OV migration network, thereby suppressing the formation/diffusion of anionic redox-mediated OVs. Consequently, superb structural integrity and improved electrochemical performance with reversible anionic redox chemistry are achieved. This work advances our understanding of the role of OVs for developing high-performance energy storage systems utilizing anionic redox.

Alloying is a powerful strategy for tuning the electronic band structure and optical properties of semiconductors. Here, we investigate the thermodynamic stability and excitonic properties of mixed-chalcogen alloys of two-dimensional (2D) hybrid organic–inorganic silver phenylchalcogenides (AgEPh; E = S, Se, Te). Using a variety of structural and optical characterization techniques, we demonstrate that the AgSePh-AgTePh system forms homogeneous alloys (AgSe_1–xTe_xPh, 0 ≤ x ≤ 1) across all compositions, whereas the AgSPh-AgSePh and AgSPh-AgTePh systems exhibit distinct miscibility gaps. Density functional theory calculations reveal that chalcogen mixing is energetically unfavorable in all cases but comparable in magnitude to the ideal entropy of mixing at room temperature. Because AgSePh and AgTePh have the same crystal structure (which is different from AgSPh), alloying is predicted to be thermodynamically preferred over phase separation in the case of AgSePh-AgTePh, whereas phase separation is predicted to be more favorable than alloying for both the AgSPh-AgSePh and AgSPh-AgTePh systems, in agreement with experimental observations. Homogeneous AgSe_1–xTe_xPh alloys exhibit continuously tunable excitonic absorption resonances in the ultraviolet–visible range, while the emission spectrum reveals competition between exciton delocalization (characteristic of AgSePh) and localization behavior (characteristic of AgTePh). Overall, these observations provide insight into the thermodynamics of 2D silver phenylchalcogenides and the effect of lattice composition on electron–phonon interactions in 2D hybrid organic–inorganic semiconductors.

Breaking the balance of the tumor microenvironment and reshaping it sustainably remain major challenges in lung cancer treatment. Here, a “tumor energy homeostasis disruptor”, the Cu₂O@Au nanozyme was developed, which exhibits excellent glucose oxidase-like activity, enabling it to be used for starvation therapy and as a mimic peroxidase for chemodynamic therapy (CDT), producing ^•OH. Cu₂O@Au nanozymes consume glucose at the tumor site to block the tumor’s energy supply, produce H₂O₂ continuously, and lower the pH to enhance the efficiency of CDT, initiating a cascade reaction that leads to a storm of reactive oxygen species (ROS). Furthermore, Cu₂O@Au nanozyme consumes glutathione and reduces the expression of the SLC7A11 (xCT) protein to decrease cancer cell uptake of cysteine, further enhancing the burst of ROS, resulting in lipid peroxidation in tumor cells and ultimately leading to ferroptosis. The excellent photothermal performance of Cu₂O@Au can further enhance CDT. Additionally, Cu₂O@Au nanozyme also has computed tomography (CT) and photothermal imaging capabilities. In conclusion, Cu₂O@Au nanozymes, acting as tumor energy homeostasis disruptor, can effectively inhibit tumor growth and successfully achieve the synergistic effects of starvation therapy/CDT/photothermal therapy (PTT). This multifunctional nanozyme holds promise for providing valuable insights and therapeutic strategies for cancer treatment.

Bimetallic Pt-based catalysts, for example, PtZn and PtSn catalysts, have gained significant attention for addressing the poor stability and low selectivity of pristine Pt catalysts over propane dehydrogenation (PDH). However, the structures of the active sites and the corresponding catalytic mechanism of PDH are still elusive. Here, we demonstrate a spatially confined Pt–Zn_mO_x@RUB-15 catalyst (where “m” is the mole ratio of Zn/Pt and RUB-15 is a layered silica), which exhibited high catalytic activity, ultrahigh selectivity (>99%), and resistance to coking at 550 °C for PDH. Significantly different from the preliminary studies over the PtZn catalysts, through the assistance of quasi-in situ X-ray photoelectron spectroscopy (XPS), in situ Fourier transform infrared spectroscopy (CO-FTIR), in situ X-ray absorption spectroscopy (XAS), and CO titration, we discovered that the active sites for PDH were the Pt–ZnO_x interfaces, characterized by a structure of Pt^δ+–Zn²⁺–O–Si. Density functional theory (DFT) calculations showed that Pt atoms positioned at Pt–ZnO_x interfaces with coordinatively unsaturated ZnO_x sites facilitate the C–H bond breaking of propane while concurrently suppressing deep dehydrogenation processes. This study suggests that engineering the interfaces of Pt–metal oxides under spatially confined conditions holds promise for developing highly efficient Pt-based catalysts for light alkane dehydrogenation.

Metal-halide perovskites (MHPs) have gained substantial interest in the energy and optoelectronics field. MHPs in nanostructure forms, such as nanocrystals and nanowires (NWs), have further expanded the horizons for perovskite nanodevices in geometry and properties. A partial anion exchange within the nanostructure, creating axial heterojunctions, has significantly augmented the potential applications. However, surface degradation and halide ion migration are deteriorating device performance. Quantitative analysis of halide metal concentration and mapping of the electrical surface potential along the operating NW device are needed to better understand ion transportation, band structure, and chemical states, which have not been experimentally reported yet. This requires a characterization approach that is capable to provide surface-sensitive chemical and electrical information at the subμm scale. Here, we used operando nanofocused X-ray photoelectron spectroscopy (nano-XPS) to study CsPbBr₃/CsPb(Br_1–xCl_x)₃ heterojunction NW devices with a spatial resolution of 120 nm. We monitored Br^– and Cl^– ion migration and comprehended the potential drop along the device during operation. Ion migration and healing of defects and vacancies are found for applied voltages of as low as 1 V. We present a model delineating band bending along the device based on precise XPS peak positions. Notably, a reversible redox reaction of Pb was observed, that reveals the interaction of migrating halide ions, vacancies, and biased metal electrodes under electrical operation. We further demonstrate how X-ray-induced surface modification can be avoided, by limiting exposure times to less than 100 ms. The results facilitate the understanding of halide ion migration in MHP nanodevices under operation.

The adsorption-conversion paradigm of polysulfides during the sulfur reduction reaction (SRR) is appealing to tackle the shuttle effect in Li-S batteries, especially based upon atomically dispersed electrocatalysts. However, mechanistic insights into such catalytic systems remain ambiguous, limiting the understanding of sulfur electrochemistry and retarding the rational design of available catalysts. Herein, we systematically explore the polysulfide adsorption-conversion essence via a geminal-atom model system to understand the catalyst roles toward an expedited SRR. A descriptor involving an electronic structure index (I_ES) and electron affinity index (I_EA) is proposed, considering the geometric and electronic dictation within a Fe/M (M: 3d-block transition metal) atomic ensemble. With the aid of theoretical computation, we managed to identify the SRR thermodynamic/kinetic trends of Fe/M moieties. Guided by these findings, we in target design a Fe/V-NC dual-atom catalyst, which harvests a minimum I_ES and maximum I_EA, accordingly demonstrating enhanced polysulfide adsorption-conversion and improved full-cell performances. Such a consistency between a computational descriptor and experimental evidence highlights the importance of an atomic catalyst screen and selection for Li-S batteries.

Periodontitis is characterized by dysbiotic biofilms, gingival inflammation, and bone resorption, highlighting the urgent need for a comprehensive approach to drug combination therapy. In this study, we introduce dynamic covalent nanonetworks (dcNNWs) synthesized through a one-pot, four-component reaction-induced self-assembly method using polyamines, 2-formylphenylboronic acid, epigallocatechin gallate, and alendronate. The formation of iminoboronate bonds drives the creation of dcNNWs, allowing controlled release in the periodontitis microenvironment. The inclusion of catechol and bisphosphonate imparts exceptional bioadhesive properties to the dcNNWs, enhancing their efficacy in preventing pathogenic bacterial biofilm formation and eliminating mature biofilms. Moreover, the dcNNWs efficiently absorb pathogen-associated molecular patterns and scavenge excess reactive oxygen species, regulating the local immune response and demonstrating anti-inflammatory effects. Additionally, the released polyphenol and alendronate from the dcNNWs alleviated inflammation and enhanced osteogenesis significantly. The detailed synergistic effects of dcNNWs in biofilm eradication, anti-inflammation, and bone remodeling, with minimal impact on healthy tissues, are confirmed in a rat model of periodontitis. With a facile synthesis process, excellent synergistic effects in periodontitis treatment, and biocompatibility, our dcNNWs present a promising and translational solution for the effective management of periodontitis.

Capsules were widely used in clinical settings for the oral delivery of various drugs, although it remains challenging to trace real-time drug release behavior and adjust dosages based on the therapeutic effect. To address these issues, we developed theranostic capsules that loaded two kinds of fluorescence nanoparticles, H₂O₂-responsive Janus Ag/Ag₂S nanoparticles (Ag/Ag₂S JNPs) and the downconversion nanoparticles (DCNPs), and the dexamethasone (Dex) drug. The Ag/Ag₂S JNPs exhibit a highly sensitive fluorescence (FL) signal at 1250 nm in response to H₂O₂, while the FL signal from the DCNPs at 1550 nm remains stable under physiological conditions. The ratio of these two FL signals formed the ratiometric FL signal, which shows correlation with the H₂O₂ concentration with a detection limit of 1.7 μM. Moreover, the capsules can be precisely delivered into the intestine, where they release the JNPs and DCNPs simultaneously. The H₂O₂-triggered ratiometric FL signals and images can diagnose inflammation and indicate its location. Meanwhile, the encapsulated Dex is released in the disease region, with ratiometric imaging allowing for real-time tracking of therapeutic efficacy and providing guidance for ongoing treatment. The theranostic capsule system provides an approach for quantitative detection of disease biomarkers and further localized release of therapeutics, thereby avoiding overdose and reducing side effects.

Chiral organic–inorganic hybrid perovskite nanocrystals have gained attention as promising materials for circularly polarized luminescence emission, owing to their high photoluminescence efficiency and superior charge-carrier mobility. However, achieving circularly polarized electroluminescence (CPEL) from mixed-phase perovskite nanocrystals remains a significant challenge. We present bichiral formamidinium lead bromide (FAPbBr₃) nanocrystals that achieve room-temperature circularly polarized light-emitting diodes (LEDs) via a synergistic effect between a chiral interior spacer (methylbenzylamine cation, MBA⁺) and a chiral surface ligand (camphorsulfonic acid, CSA). The incorporation of MBA⁺ induces chiral crystal lattices, while CSA ligands, featuring sulfonate groups, effectively passivate defects, suppress exciton spin-flip, and enhance conductivity. The resulting circularly polarized LEDs exhibit an enhanced electroluminescence asymmetry factor (g_EL) of ∼2 × 10^–3, along with an external quantum efficiency (EQE) of 3.1%. These bichiral nanocrystals represent a significant advancement in luminescence efficiency and enantioselectivity, indicating their potential for next-generation chiroptoelectronic applications.

Replacing the oxygen evolution reaction (OER) with the urea oxidation reaction (UOR) in conjunction with the hydrogen evolution reaction (HER) offers a feasible and environmentally friendly approach for handling urea-rich wastewater and generating energy-saving hydrogen. However, the deactivation and detachment of active sites in powder electrocatalysts reported hitherto present significant challenges to achieving high efficiency and sustainability in energy-saving hydrogen production. Herein, a self-supported bimetallic nickel manganese metal–organic framework (NiMn-MOF) nanosheet and its derived heterostructure composed of NiMn-MOF decorated with ultrafine Pt nanocrystals (Pt_NC/NiMn-MOF) are rationally designed. By leveraging the synergistic effect of Mn and Ni, along with the strong electronic interaction between NiMn-MOF and Pt_NC at the interface, the optimized catalysts (NiMn-MOF and Pt_NC/NiMn-MOF) exhibit substantially reduced potentials of 1.459 and −0.129 V to reach 1000 mA cm^–2 during the UOR and HER. Theoretical calculations confirm that Mn-doping and the heterointerface between NiMn-MOF and Pt nanocrystals regulate the d-band center of the catalyst, which in turn enhances electron transfer and facilitates charge redistribution. This manipulation optimizes the adsorption/desorption energies of the reactants and intermediates in both the HER and UOR, thereby significantly reducing the energy barrier of the rate-determining step (RDS) and enhancing the electrocatalytic performance. Furthermore, the urea degradation rates of Pt_NC/NiMn-MOF (96.1%) and NiMn-MOF (90.3%) are significantly higher than those of Ni-MOF and the most reported advanced catalysts. This work provides valuable insights for designing catalysts applicable to urea-rich wastewater treatment and energy-saving hydrogen production.

Optical imaging in the 1500–1700 nm region, known as near-infrared IIb (NIR-IIb), shows potential for noninvasive in vivo detection owing to its ultrahigh tissue penetration depth and spatiotemporal resolution. Rare earth-doped nanoparticles have emerged as widely used NIR-IIb probes because of their excellent optical properties. However, their downshifting emissions rarely exhibit sufficient brightness beyond 1600 nm. This study presents tetragonal-phase thulium-doped nanoparticles (Tm³⁺-NPs) with core–shell–shell structures (CSS, LiYbF₄:3%Tm@LiYbF₄@LiYF₄) that exhibit bright downshifting luminescence at 1680 nm. Enhanced luminescence is attributed to (1) the promoted nonradiative relaxation between the doping ions and (2) the maximized sensitization process. Additionally, this strategy was validated for NIR-IIb luminescence enhancement of erbium (Er³⁺)-doped NPs. After surface modification with PEGylated liposomes, tetragonal-phase Tm³⁺-NPs exhibited a prolonged blood cycle time, high colloidal stability, and good biocompatibility. Owing to the advantages of Tm³⁺-based probes in NIR-IIb imaging, in vivo thrombus detection and monitoring of angiogenesis and arteriogenesis were successfully performed in a mouse model of ischemic hind limbs.

The blood–spinal cord barrier (BSCB) tightly regulates the transport of molecules from the blood to the spinal cord. Herein, we present an approach for transient modulation of BSCB permeability and localized delivery of peptides into the spinal cord for behavior modulation with high spatial resolution. This approach utilizes optical stimulation of vasculature-targeted nanoparticles and allows delivery of BSCB-impermeable molecules into the spinal cord without significant glial activation or impact on animal locomotor behavior. We demonstrate minimally invasive light delivery into the spinal cord using an optical fiber and BSCB permeability modulation in the lumbar region. Our method of BSCB modulation allows the delivery of bombesin, a centrally acting and itch-inducing peptide, into the spinal cord and induces a rapid and transient increase in itching behaviors in mice. This minimally invasive approach enables behavior modulation without genetic modifications and is promising for delivering a wide range of biologics into the spinal cord for potential therapy with high spatiotemporal resolution.

Two-dimensional covalent organic frameworks (2D COFs), a family of crystalline materials with abundant porous structures offering nanochannels for molecular transport, have enormous potential in the applications of separation, energy storage, and catalysis. However, 2D COFs remain limited by relatively large pore sizes (>1 nm) and weak interlayer interactions between 2D nanosheets, making it difficult to achieve efficient membranes to meet the selective sieving requirements for water molecules (0.3 nm) and hydrated salt ions (>0.7 nm). Here, we report a high-performance 2D COF membrane with narrowed channels (0.7 × 0.4 nm²) and excellent mechanical performance constructed by the staggered stacking of cationic and anionic 2D COF nanosheets for selectively sieving of water molecules and hydrated salt ions. The mechanical performance has been improved by two times than that of single-phase 2D COF membranes due to the enhanced interlayer interactions between nanosheets. The stacked 2D COF membranes exhibit significantly improved monovalent salt ions rejection ratio (up to 77.9%) compared with single-phase COF membranes (∼49.2%), while maintaining comparable water permeability. The design of stacked 2D COF membranes provides a potential strategy for constructing high-performance nanoporous membranes to achieve precise molecular and ionic sieving.

Perovskite-based direct-current triboelectric nanogenerators (DC-TENGs) leveraging the tribo-photovoltaic effect have garnered significant attention for their ability to simultaneously harvest mechanical and solar energy, effectively enhancing the output performance of DC-TENGs. Herein, we innovatively construct a rolling-mode Cu/ternary cation perovskite (FA_0.945MA_0.025Cs_0.03Pb(I_0.975Br_0.025)₃) Schottky junction DC-TENGs with ultrahigh current output and excellent operational stability. The Cu/perovskite Schottky junction ensures the formation of an internal electric field, promoting carrier separation and directional movement for a stable DC output. Under AM 1.5 G illumination, the DC-TENG achieves a short-circuit current (I_sc) and current density of 408 μA and 27.2 A/m², respectively, marking a 119 times increase as compared to dark conditions and the highest reported I_sc for perovskite DC-TENGs. With over 30 min of operation, the current output remains stable. The DC-TENGs exhibit promising applications in temperature and humidity sensing and self-powered photodetection. Furthermore, by adjusting the light power density, the optimal internal output impedance of DC-TENGs can be tuned broadly from 0.9 to 132 kΩ, offering great potential for impedance matching in self-powered microelectronic components. This research provides insights into the development of multifunctional DC-TENG devices with coupled mechanical and solar energy, expanding the application scope of perovskite materials and devices.

This article describes an approach to making highly stable copper nanowire networks on any type of substrates. These nanostructured materials are highly sought after for, among other applications, the development of next-generation flexible electronics. Their high susceptibility to oxidation in air currently limits their use in the real world. Here, we develop a multistep chemical method to fabricate transparent electrodes (TEs) using Cu-based bimetallic NW networks on various substrates at room temperature. First, we synthesized homogeneous core@shell copper@nickel (Cu@Ni) NWs using a one-pot colloidal approach. After their deposition on a substrate, we exploited the exothermic nature of the reaction between the Ni oxide and hydrazine to eliminate the naturally formed metal oxide moieties and interlock the NW junctions of the network. Electrical measurements, at the single junction level, indicate that the exothermic reaction induces a reduction of resistance by up to 4 orders of magnitude. On a macroscopic scale, the resulting Cu-based NW networks feature an optical transmittance of 80% in the visible region and a sheet resistance of 10 Ω/sq with a record stability of over 2 years. This process offers a simple and efficient strategy for fabricating cost-effective, long-life electronic devices, as illustrated by a proof-of-concept integrating an optimized Cu@Ni-based TE as a flexible transparent heater.

The emergence of reconfigurable field effect transistors has introduced a more efficient method for realizing reconfigurable circuits, significantly lowering hardware overhead and enhancing versatility. However, these devices often suffer from asymmetric transfer curves, impacting logic gate performance and reliability. This work investigates the use of the van der Waals junction field effect transistor (JFET) for reconfigurable circuit applications. We present a reconfigurable JFET realized through WSe₂/MoS₂ van der Waals integrated heterojunctions with an optimized polarity gate design that effectively addresses the issues of unmatched threshold voltages between n- and p- FETs while also anchoring threshold voltages and reducing subthreshold swing. A complementary reconfigurable JFET inverter with the proposed gate design was demonstrated, showcasing excellent switching characteristics, symmetric transfer characteristics, and reduced power consumption, achieving a noise margin of 96.3% and a high gain of 153.82. The study further demonstrates the construction of reconfigurable NOR/NAND and XOR/XNOR logic gates with symmetric profiles and sharp switching, underscoring the versatility and effectiveness of the proposed approach. These findings highlight the potential of WSe₂/MoS₂ JFETs in advancing low-power, high-performance, reconfigurable electronic circuits within the CMOS framework.

Bioaccumulated silver nanoparticles (AgNPs) can undergo transformation and release toxic Ag⁺, which can be further reduced and form secondary AgNPs (Ag⁰NPs). However, the intricate interconversions among AgNPs, Ag⁺, and Ag⁰NPs remain speculative. Herein, we developed a bioimaging method by coupling the aggregation-induced emission method with the label-free confocal scattering and hyperspectral imaging techniques to quantitatively visualize the biodistribution and biotransformation of AgNPs, Ag⁰NPs, and Ag⁺ in living cells. We demonstrated that AgNPs were first dissolved in the medium, and the released Ag⁺ was converted into Ag⁰NPs with the presence of algal extracellular polymeric substances and light. Under these conditions, AgNPs alone accounted for 12.4% of the total AgNP toxicity, a percentage comparable to that of Ag⁰NPs (15.6%). However, Ag⁺ remained the primary contributor to overall AgNP toxicity. Additionally, we found that about 9.00% of the accumulated AgNPs within the algal cells were transformed after 24 h exposure. Of these transformed AgNPs, 4.70% remained as Ag⁺ forms (located in the apical region, nucleus, and pyrenoid), while 4.30% persisted as Ag⁰NP forms (located in the cytosol) that were only detectable after a 4 h exposure. We further showed that AgNP exposure upregulated algal glutathione production with a 38.3-fold increase in glutathione reductase activity, which potentially resulted in Ag⁰NP formation at the active site. Overall, this study differentiated the toxicity of AgNPs, Ag⁺, and Ag⁰NPs and directly visualized the ongoing transformation and translocation of AgNPs, Ag⁺, and Ag⁰NPs within living cells, which are critical in unveiling the toxicity mechanisms of AgNPs.

The large-scale preparation of two-dimensional (2D) materials is pivotal in unlocking their extensive potential for next-generation semiconductor device applications. Wafer-scale single crystals of a high-symmetry 2D material (e.g., graphene and molybdenum disulfide) can be achieved by seamlessly stitching the aligned domains. However, achieving the alignment of low-symmetry 2D materials remains a great challenge and is rarely reported. Rhenium disulfide (ReS₂), one of the low-symmetry 2D materials, shows considerable promise for optoelectronics, especially polarization-sensitive applications. Here, we report large-area chemical vapor deposition synthesis of highly oriented, low-symmetry monolayer ReS₂ flakes on a high-symmetry Au(111) surface, followed by seamless stitching into a centimeter-scale continuous 2D film. Cross-sectional scanning transmission electron microscopy reveals that the aligned monolayer ReS₂ flakes are guided by step edges on Au(111) surfaces along the [011̅] direction. Additionally, 2D ReS₂ can flatten Au surfaces during its growth through surface step bunching. The growth of the ReS₂ monolayer demonstrates its ability to extend across Au surface steps and facets. Thus, we have established a reliable and robust synthesis route that accommodates different surface roughness conditions. The aligned and scalable film growth of low-symmetry 2D ReS₂ significantly contributes to the in-depth understanding of epitaxial growth mechanisms for low-symmetry 2D materials, holding promise for advancing their future applications.

A surface-enhanced Raman scattering (SERS) biosensor with minimal invasiveness and high spatial resolution has been developed as a nanoendoscope to detect changes in protein concentrations at specific sites in biological tissues. While generally applicable to various tissues or proteins, the SERS nanoendoscope is demonstrated for the quantitative detection of S100β, an astrocytic protein whose plasmatic levels are known to vary in several neuropathologies such as Alzheimer’s disease, schizophrenia, Down syndrome, Parkinson’s disease and epilepsy, but for which intratissular levels have not been locally monitored, demonstrating key attributes of the SERS nanoendoscope. The SERS nanoendoscope is fabricated with densely and well-dispersed deposited gold nanoparticles modified with anti-S100β primary antibody on pulled optical fibers with a tip diameter of 700 nm, conducive to noninvasive and regiospecific detection of the S100β protein in different regions of mouse brain slices under different physiological stimuli with micrometer resolution. Quantification was performed ex vivo using SERS-active nanotags with secondary antibodies with detection limits of 5 and 7 nM in phosphate-buffered saline solution and mouse brain slice, respectively. Various physiological stimuli were then applied ex vivo to wild-type and S100β-knockout mouse brain slices to demonstrate the SERS nanoendoscope under physiological conditions. The average concentration of S100β was increased to 27, 45, and 48 nM upon N-methyl-d-aspartate, electrical, and optogenetic stimulation, respectively, statistically higher than all controls, demonstrating the ability of the SERS nanoendoscope to quantify protein release in biological tissues.

The synthetically evolved pHD family of peptides is known to self-assemble into macromolecule-sized nanopores of 2–10 nm diameter in synthetic lipid bilayers, but only when the pH is below ∼6. Here, we show that a representative family member, pHD108, has the same pH-responsive nanopore-forming activity in the endosomal membranes of living human cells, which is triggered by endosomal acidification. This enables the cytosolic delivery of endocytosed proteins and other macromolecules. Acylation of either peptide terminus significantly decreases the concentration of peptide required for macromolecule delivery to the cell cytosol while not causing any measurable cytotoxicity. Longer acyl chains are more effective. The N-terminal palmitoylated C16-pHD108 is the most potent of all of the acyl-pHD108 variants and readily delivers a cytotoxic enzyme, fluorescent proteins, and a dye-labeled dextran to the cell cytosol. C16-pHD108 forms stable monodisperse micellar nanoparticles in a buffer at pH 7 with an average diameter of around 120 nm. These nanoparticles are not cytolytic or cytotoxic because the acylated pHD peptide does not partition from the nanoparticles into cell membranes at pH 7. At pH 5, the nanoparticles are unstable, driving acylated pHD108 to bind strongly to membranes. We hypothesize that passive endocytosis of macromolecular cargo and stable peptide nanoparticles, followed by endosomal acidification-dependent destabilization of the nanoparticles, triggers the nanopore-forming activity of acylated pHD peptides in the endosomal membrane, enabling internalized macromolecules to be delivered to the cytosol.

Nanomagnetic forces deliver precise mechanical cues to biological systems through the remote pulling of magnetic nanoparticles under a permanent magnetic field. Cortical neurons respond to nanomagnetic forces with cytosolic calcium influx and event rate shifts. However, the underlying consequences of nanomagnetic force modulation on cortical neurons remain to be elucidated. Here, we integrate electrophysiological and optical recording modalities with nanomagnetic forces to characterize the in vitro functional response to mechanical cues. Neurons exposed to chitosan functionalized magnetic nanoparticles for 24 h and then exposed to magnetic fields capable of generating forces of 2–160 pN present elevated cytosolic calcium in neurons and a time-dynamic electrophysiological spike rate and magnitude response. Extracellular recordings with microelectrode arrays revealed a 2–8 pN force-specific increase in electrophysiological spiking with a trend in reduced activity following 2 min of continuous force exposure. Nanomagnetic forces in the 16–160 pN range produced increased electrophysiological activity and remained excited for up to 4 h under continuous stimulation before silencing. Furthermore, the neuronal response to nanomagnetic forces at 16–160 pN can be electrophysiologically mediated without calcium influx by altering the magnetic nanoparticle-neuron interactions. These results demonstrate that low pN nanomagnetic forces mediate neuronal function and suggest that magnetic nanoparticle interactions and force magnitudes can be harnessed to provoke different responses in cortical neurons.

Photocatalytic water splitting is a promising route to low-cost, green H₂. However, this approach is currently limited in its solar-to-hydrogen conversion efficiency. One major source of efficiency loss is attributed to the high rates of undesired side and back reactions, which are exacerbated by the proximity of neighboring oxidation and reduction sites. Nanoscopic oxide coatings have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as it cannot facilitate both half-reactions. In this work, area selective atomic layer deposition (AS-ALD) was used to selectively deposit semipermeable TiO₂ films onto model metallic cocatalysts for enhancing reaction selectivity while maintaining a high overall activity. Pt and Au were used as exemplary reduction and oxidation cocatalyst sites, respectively, where Au was deactivated toward ALD growth through self-assembled thiol monolayers while TiO₂ was coated onto Pt sites. Electroanalytical measurements of monometallic thin film electrodes showed that the TiO₂-encapsulated Pt effectively suppressed undesired H₂ oxidation and Fe(II)/Fe(III) redox reactions while still permitting the desired hydrogen evolution reaction (HER). A planar model photocatalyst platform containing patterned interdigitated arrays of Au and Pt microelectrodes was further assessed using scanning electrochemical microscopy (SECM), demonstrating the successful use of AS-ALD to enable local reaction selectivity in a dual-reaction-site (photo)electrocatalytic system. Finally, interdigitated microelectrodes having independent potential control were used to show that selectively deposited TiO₂ coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared with uncoated control samples.

Preclinical and clinical diagnostics depend greatly on medical imaging, which enables the identification of physiological and pathological processes in living subjects. It is often necessary to use contrast agents to complement anatomical data with functional information or to describe the disease phenotypically. Nanomaterials are used as contrast agents in many advanced bioimaging techniques and applications because of their high payload, physicochemical properties, improved sensitivity, and multimodality. Metals with k-edge energy within the X-ray bandwidth respond to photon counting and spectral X-ray imaging. This Perspective examines the progress made in the emerging area of nanoparticle-based k-edge contrast agents. These nano “k-edge” particles have been explored with spectral photon counting CT (SPCCT) for multiplexed molecular imaging, pushing the boundaries of resolution and capabilities of CT imaging. Design considerations, contrast properties, and biological behavior are discussed in detail. The key applications are highlighted by categorizing these nanomaterials based on their X-ray, k-edge energy, and biological properties, as well as their synthesis, functionalization, and characterization processes. The article delves into the transformative impact of nano “k-edge” particles on early disease detection and other biomedical applications. The review provides further insights into how the “k-edge signatures” of these nanoparticles combined with photon counting technique can be leveraged for quantitative, multicontrast imaging of diseases. We also discuss the status quo of clinically approved nanoparticles for imaging and highlight the challenges such as toxicity and clearance as well as promising clinical perspectives, providing a balanced view of the potential and limitations of these nanomaterials. Furthermore, we discuss the necessary future research efforts required to clinically translate nano “k-edge” particles as SPCCT contrast agents for early disease diagnosis and tracking.

Organic conducting polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has garnered enormous attention in organic electronics due to its low-cost solution processability, highly tunable conductivity, superior mechanical flexibility, and good biocompatibility together with excellent atmospheric stability. Nevertheless, limited electrical properties and unfavorable water instability of pristine PEDOT:PSS film impede its further implementation in a broad spectrum of practical applications. In this work, the successful tailoring of the intrinsic electrostatic interaction within PEDOT:PSS and consequent optimized electrical properties are enabled by a simple yet effective ionic salt post-treatment strategy. The choice of zinc di[bis(trifluoromethylsulfonyl)imide] (Zn(TFSI)₂) not only endows the post-treated PEDOT:PSS film with high electrical properties but also other compelling characteristics, including superior water stability, excellent mechanical flexibility, and fast humidity responsiveness. Multidimensional characterizations are conducted to gain in-depth insights into the mechanisms underlying such improved performance, ranging from intermolecular interactions, polymer conformations, and doping levels to microstructural characteristics. Benefiting from these versatile properties, the as-prepared freestanding Zn(TFSI)₂-post-treated PEDOT:PSS films can serve as promising candidates for high-performance polymeric materials integrated into multifunctional flexible electronics, including thermoelectric power generators, conductive hydrogels, and humidity-responsive actuators. This study demonstrates a facile methodology for the exploration of multifunctional conducting polymers, whose implications can extend across a wide range of next-generation wearable devices, bioelectronics, and soft robotics.

The existence of superconductivity (SC) appears to be established in both twisted and nontwisted graphene multilayers. However, whether their building block, single-layer graphene (SLG), can also host SC remains an open question. Earlier theoretical works predicted that SLG could become a chiral d-wave superconductor driven by electronic interactions when doped to its van Hove singularity, but questions such as whether the d-wave SC survives the strong band renormalizations seen in experiments, its robustness against the source of doping, or if it will occur at any reasonable critical temperature (T_c) have remained difficult to answer, in part due to uncertainties in model parameters. Furthermore, doping of graphene beyond its van Hove singularity remained experimentally challenging and was not demonstrated until recently. In this study, we n dope SLG past the van Hove singularity by employing Tb intercalation and derive structural models from angle-resolved photoemission spectroscopy measurements. We adopt a reliable numerical framework based on a random-phase approximation technique to investigate the emergence of unconventional SC in the heavily doped monolayer. We predict that robust d + id topological SC could arise in SLG doped by Tb, with a T_c up to 600 mK. We also employ first-principles calculations to investigate the possibility of realizing d-wave SC with other dopants, such as Li or Cs. We find that dopants that change the lattice symmetry of SLG are detrimental to the d-wave state. The stability of the d-wave SC predicted here in Tb-doped SLG could provide a valuable insight for guiding future experimental efforts aimed at exploring topological superconductivity in monolayer graphene.

Defects in chemical vapor deposition (CVD)-grown monolayer MoS₂ are unavoidable and provide a powerful approach to creating single-photon emitters and quantum information systems through localizing excitons. However, insight into the A^– trion and B/C exciton localization in monolayer MoS₂ remains elusive. Here, we investigate defect-mediated A^– trion and B/C exciton localization and relaxation in CVD-grown monolayer MoS₂ samples via transient absorption spectroscopy. The localization rate of A^– trions is five times faster than B excitons, which is attributed to the distinctions in the Bohr radius, diffusion rate, and multiphonon emission. Furthermore, we obtain unambiguous experimental evidence for the direct excitation of localized C excitons. Varying gap energy at the band-nesting region revealed by first-principles calculations explains the anomalous dependence of localized C exciton energy on delay time. We also find that the rapid dissociation of localized C excitons features a short characteristic time of ∼0.14 ps, while the measured relaxation time is much longer. Our results provide a comprehensive picture of the defect-mediated excitonic relaxation and localization dynamics in monolayer MoS₂.

Extracellular vesicles (EVs) have demonstrated considerable potential in the treatment of ischemic bone diseases, such as glucocorticoid-induced osteonecrosis of the femoral head (GIONFH). However, the clinical application of EVs faces challenges such as low yield, poor bioactivity, and lack of targeting. Herein, we have developed a platform of multiengineered extracellular vesicle mimetics (EVMs) to address these challenges. By stimulating mesenchymal stem cells (MSCs) with multibioactive ions from TS (Trisilicate, a mixture of calcium silicate, magnesium silicate, and strontium silicate), we obtained endogenously modified TS-MSCs. From these, we further prepared a large quantity of bioactive EVM_TS-MSCs through a straightforward extrusion method. Moreover, by integrating metabolic glycoengineering with click chemistry strategies, alendronate (ALN) was surface-modified on EVM_TS-MSCs to further prepare ALN-EVM_TS-MSCs. The engineered ALN-EVM_TS-MSCs demonstrated bone-targeting effects, promoting osteogenesis and angiogenesis. This promoting effect is attributed to the rich presence of miR-21 in the TS-modified EVM, which further silences PTEN to activate the PI3K/AKT signaling pathway, thereby enhancing osteogenesis and angiogenesis. Our treatment strategy for ischemic bone diseases is based on a multiengineered, biomaterial-inspired, metabolic glycoengineering, and click chemistry-based platform of EVM. This study also provides an enhanced understanding of the development and application of engineered vesicles in disease treatment.

Photothermal catalysis is an emerging field with significant potential for sustainable chemical production processes. The merger of single-atom catalysts (SACs) and photothermal catalysis has garnered widespread attention for its ability to achieve precise bond activation and superior catalytic performance. This review provides a comprehensive overview of the recent progress of SACs in photothermal catalysis, focusing on their underlying mechanisms and applications. The dynamic structural evolution of SACs during photothermal processes is highlighted, and the current advancements and future perspectives in the design, screening, and scaling up of SACs for photothermal processes are discussed. This review aims to provide insights into their continued development in this rapidly evolving field.

Viral nanoparticles (VNPs) have emerged as crucial tools in the field of biomedicine. Leveraging their biological and physicochemical properties, VNPs exhibit significant advantages in the prevention, diagnosis, and treatment of human diseases. Through techniques such as chemical bioconjugation, infusion, genetic engineering, and encapsulation, these VNPs have been endowed with multifunctional capabilities, including the display of functional peptides or proteins, encapsulation of therapeutic drugs or inorganic particles, integration with imaging agents, and conjugation with bioactive molecules. This review provides an in-depth analysis of VNPs in biomedicine, elucidating their diverse types, distinctive features, production methods, and complex design principles behind multifunctional VNPs. It highlights recent innovative research and various applications, covering their roles in imaging, drug delivery, therapeutics, gene delivery, vaccines, immunotherapy, and tissue regeneration. Additionally, the review provides an assessment of their safety and biocompatibility and discusses challenges and future opportunities in the field, underscoring the vast potential and evolving nature of VNP research.

Extracellular vesicles (EVs) possess the characteristics of their parent cells, based on which various studies have actively investigated treatments for diseases using mesenchymal stem cell-derived EVs due to their regenerative activity. Furthermore, in recent years, there have been significant efforts to engineer EVs to improve their native activities and integrate additional functions. Although both endogenous and exogenous methods are used for engineering EVs, endogenous methods may pose the problem of administering substances to cells undergoing metabolic changes, which can cause potential side effects. In addition, exogenous methods may have the limitation of losing beneficial factors inside EVs due to membrane disruption during engineering processes. Surface modification of EVs may also impair efficiency due to the presence of proteins on the EV surface. Therefore, in this study, a stable and efficient engineering method was achieved through the ethanol-mediated hybridization of EVs and functionalized lipid nanoparticles (LNPs) with a fusogenic lipid component. During hybridization, the internal bioactive factors and targeting moiety were maintained to possess the characteristics of both LNPs and EVs. The Ab-Hybrid, which was successfully synthesized through hybridization with nicotinamide-encapsulated and Col2A1 antibody-modified liposome and Transforming growth factor-β1 (TGF-β1)-overexpressed EVs, was administered to osteoarthritis (OA)-induced rats undergoing the destabilization of the medial meniscus surgery. Ultimately, the Ab-Hybrid demonstrated excellent chondroprotective and anti-inflammatory effects with targeting and long-lasting properties in OA lesions. We anticipate that this approach for manufacturing hybrid particles will serve as a valuable EV engineering method and a versatile platform technology applicable to various diseases.

Photovoltaic devices capable of reversible photovoltaic polarity through external signal modulation may enable multifunctional optoelectronic systems. However, such devices are limited to those induced by gate voltage, electrical poling, or optical wavelength by using complicated device architectures. Here, we show that the photovoltaic polarity is also switchable with the intensity of incident light. The modulation in light intensity induces photovoltaic polarity switching in geometrically asymmetric MoS₂ Schottky photodiodes, explained by the asymmetric lowering of the Schottky barrier heights due to the trapping of photogenerated holes at the MoS₂/Cr interface states. An applied gate voltage can further modulate the carrier concentration in the MoS₂ channel, providing a method to tune the threshold light intensity of polarity switching. Finally, a bidirectional optoelectronic logic gate with “AND” and “OR” functions was demonstrated within a single device.

Flash Joule heating has been used as a versatile solid-state synthesis method in the production of a wide range of products, including organic, inorganic, and ceramic products. Conventional flash Joule heating systems are large and customized, presenting significant barriers in the cost of assembly, the expertise needed to operate, and uniformity of results between different systems. Even laboratory-scale flash Joule heating systems struggle to operate above 10 g capacity, and they suffer from poor temperature controllability. We present here the use of commercial off-the-shelf arc welders as a superior alternative to standard flash Joule heating systems due to their low cost ($120), ease of use, compact size, high temperature controllability, and tunability. We demonstrate the gram-scale synthesis of a variety of organic and ceramic species using these systems. With the addition of another reactor configuration for only $260, we scale up the synthesis of these products to record rates for the laboratory scale, achieving a production rate of 3 kg/h for graphene and kilogram-per-day production rates for SiC, carbon nanotubes, SnSe₂, and SnS₂.

High-energy lithium (Li)-based batteries, especially rechargeable Li–CO₂ batteries with CO₂ fixation capability and high energy density, are desirable for electrified transportation and other applications. However, the challenges of poor stability, low energy efficiency, and leakage of liquid electrolytes hinder the development of Li–CO₂ batteries. Herein, a highly conductive and stable metal–organic framework-encapsulated ionic liquid (IL@MOF) electrolyte system is developed for quasi-solid-state Li–CO₂ batteries. Benefiting from the host–guest interaction of MOFs with open micromesopores and internal IL, the optimized IL@MOF electrolytes exhibit a high ionic conductivity of 1.03 mS cm^–1 and a high transference number of 0.80 at room temperature. The IL@MOF electrolytes also feature a wide electrochemical stability window (4.71 V versus Li⁺/Li) and a wide working temperature (−60 °C ∼ 150 °C). The IL@MOF electrolytes also enable Li⁺ and electrons transport in the carbon nanotubes-IL@MOF (CNT-IL@MOF) solid cathodes in quasi-solid-state Li–CO₂ batteries, delivering a high specific capacity of 13,978 mAh g^–1 (50 mA g^–1), a long cycle life of 441 cycles (500 mA g^–1 and 1000 mAh g^–1), and a wide operation temperature of −60 to 150 °C. The proposed MOF-encapsulated IL electrolyte system presents a powerful strategy for developing high-energy and highly safe quasi-solid-state batteries.

Chemical exchange saturation transfer magnetic resonance imaging (CEST MRI) enables the imaging of many endogenous and exogenous compounds with exchangeable protons and protons experiencing dipolar coupling by using a label-free approach. This provides an avenue for following interesting molecular events in vivo by detecting the natural protons of molecules, such as the increase in amide protons of proteins in brain tumors and the concentration of drugs reaching the target site. Neither of these detections require metallic or radioactive labels and thus will not perturb the molecular events happening in vivo. Yet, magnetization transfer processes such as chemical exchange and dipolar coupling of protons are sensitive to the local environment. Hence, the use of nanocarriers could enhance the CEST contrast by providing a relatively high local concentration of contrast agents, considering the portion of the protons available for exchange, optimizing the exchange rate, and utilizing molecular interactions. This review provides an overview of these factors to be considered for designing efficient CEST contrast agents (CAs), and the molecular events that can be imaged using CEST MRI during disease progression and treatment, as well as the nanocarriers for drug delivery and distribution for the evaluation of treatments.

Silica polymerization from its soluble monomers is fundamental to many chemical processes. Although industrial methods require harsh conditions and concentrated precursors, biological silica precipitation occurs under ambient conditions from dilute solutions. The hallmark of biosilica is the presence of amine-rich organic macromolecules, but their functional role remains elusive. Here, we show a pH-dependent stimulatory effect of such polyamines on silica polymerization. Notably, this process is decoupled from the saturation degree, allowing the synthesis of polymer–silica hybrid products with controlled network morphologies from undersaturated solutions. The data suggest a two-step phase separation process. First, an associative liquid–liquid phase separation forms a micrometer-size dense phase. Second, silica undergoes a liquid-to-solid transition in the supersaturated condensates to form a bicontinuous silica structure. This study can inspire “soft chemistry” routes to design organic–inorganic nanomaterials with regulatory principles optimized by evolution.

Ionic liquids (ILs) are a promising class of electrolytes with a unique combination of properties, such as extremely low vapor pressures and nonflammability. Doping ILs with alkali metal salts creates an electrolyte that is of interest for battery technology. These salt-in-ionic liquids (SiILs) are a class of superconcentrated, strongly correlated, and asymmetric electrolytes. Notably, the transference numbers of the alkali metal cations have been found to be negative. Here, we investigate Na-based SiILs with a surface force apparatus, X-ray scattering, and atomic force microscopy. We find evidence of confinement-induced structural changes, giving rise to long-range interactions. Force curves also reveal an electrolyte structure consistent with our predictions from theory and simulations. The long-range steric interactions in SiILs reflect the high aspect ratio of compressible aggregates at the interfaces rather than the purely electrostatic origin predicted by the classical electrolyte theory. This conclusion is supported by the reported anomalous negative transference numbers, which can be explained within the same aggregation framework. The interfacial nanostructure should impact the formation of the solid electrolyte interphase in SiILs.

Twisted two-dimensional (2D) material heterostructures provide an exciting platform for investigating fundamental physical phenomena. Many of the most interesting behaviors emerge at small twist angles, where the materials reconstruct to form areas of perfectly stacked crystals separated by partial dislocations. However, understanding the properties of these systems is often impossible without correlative imaging of their local reconstructed domain configuration, which exhibits random variations due to disorder and contamination. In particular, visualization of the local domain configuration allows determination of the local twist angle and, hence, the local lattice strain. Here, we demonstrate a simple and widely accessible route to visualize domains in the as-produced twisted transition metal dichalcogenide (TMD) heterostructures using electron channeling contrast imaging (ECCI) in scanning electron microscopy (SEM). This nondestructive approach is compatible with conventional substrates and allows domains to be visualized even when sealed beneath an encapsulation layer. Complementary theoretical calculations reveal how a combination of elastic and inelastic scattering leads to contrast inversions at the specified detector scattering angles and sample tilts. We demonstrate that optimal domain contrast is therefore achieved by maximizing signal collection while avoiding contrast inversion conditions.

The quantum-dot-in-perovskite matrix (DIM) is an emerging class of semiconductors for optoelectronics enabled by their complementary charge transport properties and stability improvements. However, a detailed understanding of the pure electrical properties in DIM is still in its early stage. Here, we developed PbS quantum dot-in-CsSnI₃ matrix solids exhibiting improved electrical properties and enhanced stability. PbS incorporation reduces the tensile strain of DIM films compared to that of pristine CsSnI₃, consequently increasing the electrical conductivity. Electrical conductivity is tunable between 20 and 130 S/cm as a function of PbS concentration. Notably, a decoupling of electrical conductivity and Seebeck coefficient is observed upon PbS addition into the perovskite matrix, which is attractive for thermoelectric applications. Density functional theory analysis reveals that at low concentrations of PbS, light holes/electrons govern the overall transport properties in DIM, while heavy holes/electrons begin to dominate as the PbS concentration increases. Understanding the electrical properties would help for designing DIMs with specific properties for various technological applications.

Realizing tunable functional materials with built-in nanoscale heat flow directionality represents a significant challenge that could advance thermal management strategies. Here we use spatiotemporally resolved thermoreflectance to visualize lateral thermal transport anisotropy in self-assembled supercrystals of anisotropic Au nanocrystals. Correlative electron and thermoreflectance microscopy reveal that nano- to mesoscale heat predominantly flows along the long-axis of the anisotropic nanocrystals, and does so across grain boundaries and curved assemblies while voids disrupt heat flow. We finely control the anisotropy via the aspect ratio of constituent nanorods, and it exceeds the aspect ratio for nanobipyramid supercrystals and certain nanorod arrangements. Finite element simulations and effective medium modeling rationalize the emergent anisotropic behavior in terms of a simple series resistance model, further providing a framework for estimating thermal anisotropy as a function of material and structural parameters. Self-assembly of colloidal nanocrystals promises an interesting route to direct heat flow in a wide range of applications that utilize this important class of materials.

The collective behavior of the shortest DNA oligomers in high concentration aqueous solutions is an unexplored frontier of DNA science and technology. Here we broaden the realm of DNA nanoscience by demonstrating that single-component aqueous solutions of the DNA 4-base oligomer GCCG can spontaneously organize into three-dimensional (3D) periodic mesoscale frameworks. This oligomer can form B-type double helices by Watson–Crick (WC) pairing into tiled brickwork-like duplex strands, which arrange into mutually parallel arrays and form the nematic and columnar liquid crystal phases, as is typical for long WC chains. However, at DNA concentrations above 400 mg/mL, these solutions nucleate and grow an additional mesoscale framework phase, comprising a periodic network on a three-dimensional body-centered cubic (BCC) lattice. This lattice is an array of nodes (valence-8, each formed by a pair of quadruplexes of GCCG terminal Gs), connected with a separation of 6.6 nm by struts (6-GCCG-long WC duplexes). This 3D-ordered DNA framework is of low density (DNA volume fraction ∼0.2), but due to its 3D crystal structure, it is osmotically incompressible over its phase range. Atomistic simulations confirm the stability of such structures, which promise to form the basis of families of simply and inexpensively made nanoscale frameworks for templating and selection applications.

Structures such as 3D buckling have been widely used to impart stretchability to devices. However, these structures have limitations when applied to piezoelectric devices due to the uneven distribution of internal strain during deformation. When strains with opposite directions simultaneously affect piezoelectric materials, the electric output can decrease due to cancellation. Here, we report an electrode design tailored to the direction of strain and a circuit configuration that prevents electric output cancellation. These designs not only provide stretchability to piezoelectric nanogenerators (PENGs) but also effectively minimize electric output loss, achieving stretchable PENGs with minimal energy loss. These improvements were demonstrated using an inorganic piezoelectric material (PZT thin film) with a high piezoelectric coefficient, achieving a substantial maximum output power of 8.34 mW/cm³. Theoretical modeling of the coupling between mechanical and electrical properties demonstrates the dynamics of energy harvesting, emphasizing the electrode design. In vitro and in vivo experiments validate the device’s effectiveness in biomechanical energy harvesting. These results represent a significant advancement in stretchable PENGs, offering robust and efficient solutions for wearable electronics and biomedical devices.

Realizing Majorana Fermions has always been regarded as a crucial and formidable task in topological superconductors. In this work, we report a physical mechanism and a material platform for realizing Majorana zero modes (MZMs). This material platform consists of open circular helix molecule (CHM) proximity coupled with an s-wave superconductor (under an external magnetic field) or interconnected-CHM chain coupled with a phase-bias s-wave superconducting heterostructure (without any external magnetic field). MZMs generated here are tightly associated with the structural chirality in CHMs. Notably, the left- and right-handedness results in completely opposite Majorana polarization (MP), leading us to refer to this phenomenon as chirality-induced MP (CIMP). Importantly, the local CIMP is closely linked to chirality-induced spin polarization, providing us with an effective way to regulate MZMs through the chirality-induced spin selectivity (CISS) effect. Furthermore, MZMs can be detected by the spin-polarized current measurements related to the CISS in chiral materials.

Collective excitations of bound electron–hole pairs, i.e., excitons, are ubiquitous in condensed matter systems, and it has been shown that they can strongly couple to other degrees of freedom, such as spin, orbital, and lattice. Among van der Waals materials with pronounced excitonic responses, CrSBr has attracted significant interest due to a very large energy shift of its fundamental bright exciton (at 1.36 eV) under an external magnetic field. This effect has been associated with an increased interlayer electronic hopping when the magnetic order is switched from antiferromagnetic to ferromagnetic by an external magnetic field, enabling its optical detection. In this work, we report the observation of a second bright excitonic resonance (at 1.76 eV), displaying a 5-fold enhancement of the magnetically induced energy shift to ∼100 meV, which we associate to a decreased spatial localization and increased interband nature compared to the fundamental exciton. Moreover, we show how the light-matter interaction reaches the ultrastrong regime where this exciton hybridizes with the cavity modes of photons confined to CrSBr flakes, forming polaritons with a Rabi splitting of ℏΩ_R ≃ 372 meV, of the same order of magnitude as the one reported for the first exciton. These results expand the understanding of the relationship between the optical response and band structure of CrSBr and clarify the essential ingredients for optimizing magneto-electronic coupling for applications.

One of the important factors leading to lithium dendrites is a slow lithium-ion mass transport and imbalanced distribution of the Li⁺ concentration and nuclei sites on the anode surface. To achieve uniform lithium deposition during the charge and discharge process, we introduce a homemade new copolymer (with the quaternary ammonium group N₃R⁺I^– on its side chain as the main functional group), named P35, as a functional electrolyte additive to regulate the lithium deposition. Theoretical calculations show that under the strong coordinating interaction between I^– and N₃R⁺, P35 preferentially adsorbs onto the lithium foil surface, effectively countering the adsorption of lithium salt anions such as PF₆^–. Moreover, the positive charge carried by the quaternary ammonium salt group of P35 could interact with PF₆^– to limit their mobility. Consequently, the dipole interaction on lithium ions is diminished, leading to an enhancement in the transport rate and a decrease in the concentration gradient of lithium ions. Furthermore, a more efficient SEI was formed due to the dual charges electrostatic shield formed by N₃R⁺I^–. Li–Li symmetric cells and Li–LiFePO₄ full cells assembled with electrolytes with P35 exhibit better rate performance, smaller polarization, and smoother deposition morphology in comparison to the cells without the P35 additive.

Chronic exposure of the liver to multiple insults culminates in the development of metabolic dysfunction-associated steatohepatitis (MASH), a complicated metabolic syndrome characterized by hepatic steatosis and inflammation, typically accompanied by progressive fibrosis. Despite extensive clinical evaluation, there remain challenges in MASH drug development, which are primarily due to unsatisfactory efficacy and limited specificity. Strategies to address the unmet medical need for MASH with fibrosis before it reaches the irreversible stage of decompensated cirrhosis are critically needed. Herein, we developed an mRNA-mediated liver-specific antibody therapy for MASH and hepatic fibrosis using a targeted lipid nanoparticle (LNP) delivery system. When encapsulated with IL-11 single-chain variable fragment (scFv)-encoded mRNA, the targeted AA3G LNP (termed mIL11-scFv@AA3G) specifically accumulated in the liver and secreted IL-11 scFv to neutralize overexpressed IL-11 in hepatic environments, thus inhibiting the IL-11 signaling pathway in hepatocytes and hepatic stellate cells. As a preventative regimen, systemic administration of mIL11-scFv@AA3G reversed MASH and prevented the progression to fibrosis in a murine model of early MASH. Notably, mIL11-scFv@AA3G exhibited superior efficacy compared to systemic administration of IL-11 scFv alone, attributed to the sustained antibody expression in the liver, which lasted 18-fold longer than that of IL-11 scFv. When tested in the MASH model with fibrosis, mIL11-scFv@AA3G effectively ameliorated steatosis and resolved fibrosis and inflammation. These findings present a versatile LNP platform targeting liver cell subtypes for the sustained expression of therapeutic antibodies to treat MASH and fibrosis. The developed mRNA-mediated liver-specific antibody therapy offers a promising approach for addressing MASH and holds the potential for expansion to various other diseases.

Electrostatically stabilized nanocrystals (NCs) and, in particular, quantum dots (QDs) hold promise for forming strongly coupled superlattices due to their compact and electronically conductive surface ligands. However, studies of the colloidal dispersion and interparticle interactions of electrostatically stabilized sub-10 nm NCs have been limited, hindering the optimization of their colloidal stability and self-assembly. In this study, we employed small-angle X-ray scattering (SAXS) experiments to investigate the interparticle interactions and arrangement of PbS QDs with thiostannate ligands (PbS–Sn₂S₆^4–) in polar solvents. The study reveals significant deviations from the ideal solution behavior in electrostatically stabilized QD dispersions. Our results demonstrate that PbS–Sn₂S₆^4– QDs exhibit long-range interactions within the solvent, in contrast to the short-range steric repulsion characteristic of PbS QDs with oleate ligands (PbS-OA). Introducing highly charged multivalent electrolytes screens electrostatic interactions between charged QDs, reducing the length scale of the repulsive interactions. Furthermore, we calculated the second virial (B₂) coefficients from SAXS data, providing insights into how surface chemistry, solvent, and size influence pair potentials. Finally, we explore the influence of long-range interparticle interactions of PbS–Sn₂S₆^4– QDs on the morphology of films produced by drying or spin-coating colloidal solutions. The long-range repulsive term of PbS–Sn₂S₆^4– QDs promotes the formation of amorphous films, and screening the electrostatic repulsion by the addition of an electrolyte enables the formation of crystalline domains. These findings highlight the critical role of NC–NC interactions in tailoring the properties of functional materials made of colloidal NCs.

Triple-negative breast cancer (TNBC) is the most aggressive and lethal subtype of breast cancer among women. Chemotherapy acts as the standard regimen for TNBC treatment but suffers from limited drug accumulation in tumor regions and undesired side effects. Herein, we developed a synergistic strategy by combining a red blood cell (RBC) membrane-liposome hybrid nanovesicle with short-term fasting (STF) for improved chemotherapy of TNBC. The biomimetic nanovesicles exhibited reduced phagocytosis by macrophages while displaying a significant increase in tumor cell uptake through caveolae/raft-mediated endocytosis under nutrient-deprivation conditions. Importantly, drug-loaded nanovesicles and STF treatment synergistically increased the cytotoxicity of tumor cells by inhibiting their cell cycles and aerobic glycolysis as well as amplifying the reactive oxygen species (ROS) and autophagosomes generation. In the STF-treated mice, biomimetic nanovesicles greatly improved the antitumor efficacy at a lower drug dosage and inhibited the undesired metastasis of TNBC. Overall, we demonstrated that biomimetic nanovesicles synergizing with STF therapy serve as a promising therapeutic strategy for enhanced chemotherapy of malignant TNBC.

Modulating the optical response of fluorescent nanoparticles through rational modification of their surface chemistry can yield distinct optical signatures upon the interaction with structurally related molecules. Herein, we present a method for tuning the fluorescence response of single-walled carbon nanotubes (SWCNTs) toward dopamine (DA) and serotonin, two structurally related monoamine-hydroxylated aromatic neurotransmitters, by introducing oxygen defects into (6,5) chirality-enriched SWCNTs suspended by sodium cholate (SC). This modification facilitated opposite optical responses toward these neurotransmitters, where DA distinctly increased the fluorescence of the defect-induced emission of SWCNTs (D-SWCNTs) 6-fold, while serotonin notably decreased it. In contrast, pristine, defect-free SWCNTs exhibited similar optical responses to both neurotransmitters. The underlying mechanisms for the divergent fluorescence response were found to be polydopamine (PDA) surface adsorption in the case of the fluorescence enhancement in response to DA, while the fluorescence decrease in response to serotonin was attributed to enhanced solvent relaxation effects in the presence of defects. Importantly, the divergent optical response of D-SWCNTs to DA and serotonin, via the introduction of defects, was validated in complex biological environments such as serum. Further, the generality of our approach was confirmed by the demonstrations of a divergent fluorescence response of D-SWCNTs suspended by an additional dispersant, namely lipid–polyethylene glycol (PEG). This study offers promising avenues for the broad applicability of surface functionalization of SWCNTs to achieve divergent responses toward structurally related molecules and advance applications in sensing, imaging, and diagnostic technologies.

The inflammatory immune microenvironment is responsible for atherosclerotic plaque erosion and rupture. Near-infrared-II (NIR-II) fluorescence imaging has the potential to continuously monitor the spatiotemporal changes in the plaque immune microenvironment. Herein, we constructed three different NIR-II probes based on benzo[1,2-c;4,5-c’]bis[1,2,5]thiadiazole-4,7-bis(9,9-dioctyl-9H-fluoren-2-yl)thiophene (denoted as BBT-2FT): VHPK/BBT-2FT NPs, where VHPK is a specific peptide targeting vascular cell adhesion molecule-1; iNOS/BBT-2FT NPs for modulating the polarization of M1 macrophages by inducible NO synthase (iNOS) antibodies; and Arg-1/BBT-2FT for counterbalancing the inflammatory responses of M1 macrophages. These tracers enable precise tracking of atherosclerotic plaques and M1 and M2 macrophages through NIR-II imaging. VHPK/BBT-2FT NPs can accurately trace atherosclerotic plaques at various stages. Arg-1/BBT-2FT NPs precisely located M2 macrophages in the early plaque microenvironment with upregulation of peroxisome proliferator-activated receptor γ (PPAR-γ), signal transducer and activator of transcription (STAT) 6, and ATP-binding cassette transporter A1 (ABCA1), indicating that M2 macrophage polarization is crucial for early plaque lipid clearance. Meanwhile, iNOS/BBT-2FT NPs accurately tracked M1 macrophages in the advanced plaque microenvironment. The results showed that M1 macrophage polarization induces the formation of an inflammatory microenvironment through anaerobic glycolytic metabolism and pyroptosis in the advanced hypoxic plaque microenvironment, as indicated by the upregulation of hypoxia-inducible factor 1 alpha (HIF-1α), STAT1, NOD-, LRR-, and pyrin domain-containing protein 3 (NLRP3), pyruvate dehydrogenase kinase 1 (PDK1), and glucose transporter 1 (GLUT-1). Combining immunological approaches with NIR-II imaging has revealed that hypoxia-induced metabolic reprogramming of macrophages is a key factor in dynamic changes in the immune microenvironment of atherosclerotic plaques. Furthermore, our strategy shows the potential for real-time diagnosis and clinical prevention of unstable plaque rupture in atherosclerosis.

Inducing trained immunity in macrophages is an increasingly promising strategy for preventing cancer development. However, it has not been investigated whether trained immunity in tumor-associated macrophages (TAMs) can be initiated for antitumor applications. Here, we provide a practical strategy that utilizes the macrophage membrane (M) to camouflage Bacillus Calmette-Guérin (M@BCG), endowing it with the capability to selectively target tumors and efficiently induce trained immunity for TAMs. Using a mouse model of Lewis lung carcinoma, we show that the introduction of macrophage membrane increases BCG’s accumulation in orthotopic lung cancer tissues compared with naked BCG. The superior tumor-targeting ability can augment BCG-mediated trained immunity in TAMs, leading to a robust activation of immune responses. Furthermore, macrophage depletion and adoptive transfer of BCG-trained TAM experiments demonstrate that the antitumor activity of M@BCG is dependent on the trained immunity of TAMs. More importantly, intravenous administration of M@BCG can synergistically reinforce the antitumor activity of immune checkpoint blockade without causing systemic toxicity. Taken together, our study demonstrates the successful initiation of trained immunity in TAMs using M@BCG, which exhibits prominent antitumor performance through immune activation.

Electron–hole recombination and exogenous local hypoxia both impede the effectiveness of thermoelectric tumor catalytic therapy. Here, a thermoelectric heterojunction (Pt-TiO_2–x/Ti₃C₂T_x-PEG) was developed to enhance charge carrier separation and alleviate tumor hypoxia. By incorporating titanium oxide with oxygen vacancies and platinum single atoms onto Ti₃C₂T_x MXene, we not only improve the charge separation efficiency but also prevent the recombination of positive and negative charges generated by the thermoelectric effect, leading to an increased production of reactive oxygen species (ROS). Furthermore, the Pt SAs exhibited excellent catalase-mimicking (CAT-mimicking) activity, catalyzing hydrogen peroxide to generate oxygen and alleviating the hypoxic tumor microenvironment. Titanium oxide with oxygen vacancies also serves as a sonosensitizer for sonodynamic therapy (SDT), enhancing ROS generation in collaboration with thermoelectric catalytic therapy. Moreover, the photothermal conversion efficiency of Pt-TiO_2–x/Ti₃C₂T_x-PEG is augmented by Pt SAs with a surface plasmon resonance effect, further boosting CAT-mimicking activity and thermoelectric catalytic therapy efficacy. This tumor-specific thermoelectric heterojunction integrates thermoelectric therapy, SDT, and photothermal therapy, demonstrating excellent tumor suppression efficacy both in vitro and in vivo. Therefore, this study offers highly valuable and promising insights into utilizing photothermoelectric/ultrasound-mediated methods for cancer treatment.

Ultraflexible neural electrodes have shown superior stability compared with rigid electrodes in long-term in vivo recordings, owing to their low mechanical mismatch with brain tissue. It is desirable to detect neurotransmitters as well as electrophysiological signals for months in brain science. This work proposes a stable electronic interface that can simultaneously detect neural electrical activity and dopamine concentration deep in the brain. This ultraflexible electrode is modified by a nanocomposite of reduced graphene oxide (rGO) and poly(3,4-ethylenedioxythiophene):poly(sodium 4-styrenesulfonate) (rGO/PEDOT:PSS), enhancing the electrical stability of the coating and increasing its specific surface area, thereby improving the sensitivity to dopamine response with 15 pA/μM. This electrode can detect dopamine fluctuations and can conduct long-term, stable recordings of local field potentials (LFPs), spiking activities, and amplitudes with high spatial and temporal resolution across multiple regions, especially in deep brain areas. The electrodes were implanted into the brains of rodent models to monitor the changes in neural and electrochemical signals across different brain regions during the administration of nomifensine. Ten minutes after drug injection, enhanced neuronal firing activity and increased LFP power were detected in the motor cortex and deeper cortical layers, accompanied by a gradual rise in dopamine levels with 192 ± 29 nM. The in vivo recording consistently demonstrates chronic high-quality neural signal monitoring with electrochemical signal stability for up to 6 weeks. These findings highlight the high quality and stability of our electrophysiological/electrochemical codetection neural electrodes, underscoring their tremendous potential for applications in neuroscience research and brain–machine interfaces.

Tunneling nanotubes (TNTs), submicrometer membranous channels that bridge and connect distant cells, play a pivotal role in intercellular communication. Organelle transfer within TNTs is crucial in regulating cell growth, signal transmission, and disease progression. However, precise control over individual organelle transport within TNTs remains elusive. In this study, we introduce an optical technique that harnesses TNTs as biophotonic conveyors for the directional transport of individual organelles between cells. By utilizing near-infrared light propagating along the TNTs, optical forces were exerted on the organelles, enabling their active transport in a predetermined direction and at a controlled velocity. As a potential application, TNT conveyors were employed to inhibit mitochondrial hijacking from immune cells to cancer cells, thereby activating immune cells and suppressing cancer cell growth. Furthermore, neural modulation was achieved by transporting mitochondria and neurotransmitter-containing vesicles between neurons via TNT conveyors and axonal conveyors, respectively. This study presents a robust and precise approach to immune activation and neural regulation through the manipulation of organelle transfer at the subcellular level.

Hot electrons (HEs) represent out-of-equilibrium carriers that are capable of facilitating reactions which are inaccessible under conventional conditions. Despite the similarity of the HE process to catalysis, optimization strategies such as orbital alignment and adsorption kinetics have not received significant attention in enhancing the HE-driven reaction yield. Here, we investigate catalytic effects in HE-driven reactions using a compositional catalyst modification (CCM) approach. Through a top-down alloying process and systematic characterization, using electrochemical, photodegradation, and ultrafast spectroscopy, we are able to disentangle chemical effects from competing electronic phenomena. Correlation between reactant energetics and the HE reaction yield demonstrates the crucial role of orbital alignment in HE catalytic efficiency. Optimization of this parameter was found to enhance HE reaction efficiency 5-fold, paving the way for tailored design of HE-based catalysts for sustainable chemistry applications. Finally, our study unveils an emergent ordering effect in photocatalytic HE processes that imparts the catalyst with an unexpected polarization dependence.

Polymers with microstructure patterns are crucial to many applications, such as separation, optics, electronics, metamaterials, etc. However, introducing microstructure patterns with diverse morphologies and feature sizes ranging from nanometers to micrometers into large-area polymers remains a significant challenge. Here, we design a material system that enables digital programming microphase separation in a polymer network to generate microstructure patterns. The polymer network is engineered to allow digital programming of local modulus, which arrests the length scale of microphase separation to generate various microstructures. These local modulus-regulated microstructures exhibit either bicontinuous or sea–island morphology and have various feature sizes ranging from ∼100 nm to several micrometers. Using household devices of an ink printer and an ultraviolet light lamp, the microstructure patterns can be programmed with fine resolutions (∼100 μm) over large areas (≫100 mm). The locally varied microstructures have different capabilities to scatter light and result in a visible pattern. We further demonstrate this design with a soft anticounterfeiting device. This approach of digital programming microphase separation in polymer networks is applicable to various polymers and provides a platform for designing many other functional devices.

Electrochemical conversion of carbon and nitrogen sources into valuable chemicals provides a promising strategy for mitigating CO₂ emissions and tackling pollutants. However, efficiently scaling up C–N products beyond basic compounds like urea remains a significant challenge. Herein, we upgrade the C–N coupling for acetamide synthesis through coreducing CO and nitrate (NO₃^–) on atomic-scale Cu dispersed on boron nitride (Cu/BN) nanosheets. The specific form of Cu, such as single atom, nanocluster, and nanoparticles, endows Cu/BN different adsorption capacity for CO and NO₃^–, thereby dictating the catalytic activity and selectivity for acetamide formation. The Cu nanocluster-anchored BN (Cu NCs/BN) catalyst achieves an industrial-level current density of 178 mA cm^–2 for the C–N coupling reaction and an average acetamide yield rate of 137.0 mmol h^–1 g_cat.^–1 at −1.6 V versus the reversible hydrogen electrode. Experimental and theoretical analyses uncover the pivotal role of the strong electronic interaction between Cu nanoclusters and BN, which activates CO and NO₃^–, facilitates the formation of key *CCO and *NH₂ intermediates, and expedites the C–N coupling pathway to acetamide. This work propels the development of atomic structure catalysts for the efficient conversion of small molecules to high-value chemicals through electrochemical processes.

Acute liver failure (ALF) is a serious global disease characterized by rapid onset and high mortality. Currently, the clinical treatment of ALF faces considerable hurdles due to limited medication options and the scarcity of liver transplants. Despite biomacromolecules such as hepatocyte growth factor (HGF) and glutathione (GSH) having been applied for ALF symptom relief in the clinic, they still face substantial challenges including poor stability, difficulty in acting on intracellular targets, and inadequate therapeutic outcome. In this work, by taking advantage of the innate targeting and regenerative capabilities of mesenchymal stem cells (MSCs), we harnessed MSC-derived exosomes as natural bioactive carriers for the simultaneous delivery of HGF and GSH, forming a fully bioactive nanodrug termed HG@Exo. Impressively, the HG@Exo demonstrated potent therapeutic effects against both carbon tetrachloride (CCl₄)- and extreme hepatectomy-induced ALF through multiple mechanisms, including regulation of oxidative stress, reduction of inflammation, and promotion of hepatocyte regeneration, which were facilitated by its inflammation-targeting to damaged liver tissues. Furthermore, an FDA-approved near-infrared fluorescent dye, indocyanine green (ICG), has been incorporated into the exosomes (HGI@Exo) to endow them with real-time in vivo tracking capability, which showed favorable liver accumulation of the HGI@Exo in both CCl₄- and surgery-induced ALF animal models, providing crucial insights into their biodistribution and therapeutic efficacy. Overall, the presented fully bioactive nanodrugs with targeting and theranostic abilities hold significant promise for potentiating the therapeutic efficacy of biomacromolecules for the improved treatment of ALF and other inflammatory diseases.

The development and comprehensive understanding of nickel chalcogenides are critical since they constitute a class of efficient electro(pre)catalysts for the oxygen evolution reaction (OER) and value-added organic oxidations. This study introduces a knowledge-based facile approach to analogous NiE (E = S, Se, Te) phases, originating from molecular β-diketiminato [Ni₂E₂] complexes and their application for OER and organic oxidations. The recorded activity trends for both target reactions follow the order NiSe > NiS > NiTe. Notably, NiSe displayed efficient performance for both OER and the selective oxidation of benzyl alcohol and 5-hydroxymethylfurfural, exhibiting stability in OER for 11 days under industrially pertinent conditions. Comprehensive analysis, including quasi in situ X-ray absorption and Raman spectroscopy, in combination with several ex situ techniques, revealed a material reconstruction process under alkaline OER conditions, involving chalcogen leaching. While NiS and NiSe experienced full chalcogen leaching and reconstruction into Ni^III/IV oxyhydroxide active phases with intercalated potassium ions, the transformation of NiTe is incomplete. This study highlights the structure–activity relationship of a whole series of analogous nickel chalcogenides, directly linking material activity to the availability of active sites for catalysis. Such findings hold great promise for the development of efficient electrocatalysts for a wide range of applications, impacting various industrial processes and sustainable energy solutions.

Although dendritic cell (DC)-mediated immunotherapies are effective options for immunotherapy, traditional DC vaccines are hampered by a variety of drawbacks such as insufficient antigen delivery, weak lymph node homing, and the risk of living cell transfusion. To address the above-mentioned issues, we developed a personalized DC-mimicking nanovaccine (HybridDC) that enhances antigen presentation and elicits effective antitumor immunity. The biomimetic nanovaccine contains cell membranes derived from genetically engineered DCs, and several cellular components are simultaneously anchored onto these membranes, including CC-chemokine receptor 7 (CCR7), tumor-associated antigenic (TAA) peptide/tumor-derived exosome (TEX), and relevant costimulatory molecules. Compared with previous vaccines, the HybridDC vaccine showed an increased ability to target lymphoid tissues and reshape the immune landscape in the tumor milieu. HybridDC demonstrated significant therapeutic and prophylactic efficacy in poorly immunogenic, orthotopic models of glioma. Furthermore, the HybridDC vaccine potentiates the therapeutic efficacy of immune checkpoint blockade (ICB) therapy, providing a potential combination strategy to maximize the efficacy of ICB. Specifically, HybridDC can induce long-term protective immunity in memory T cells. Overall, the HybridDC vaccine is a promising platform for personalized cancer vaccines and may offer a combinational modality to improve current immunotherapy.

Brain metastasis contributes substantially to the morbidity and mortality of various malignancies and is characterized by high chemoresistance. Intracellular communication between carcinoma cells and astrocytes through gap junctions, which are assembled mainly by the connexin 43 protein, has been shown to play a vital role in this process. However, effectively blocking the gap junctions between the two cell types remains extremely challenging because of insufficient drug delivery to the target site. Herein, we designed a connexin blocker-carbenoxolone (CBX)-loaded biomimetic liposomal system with artificial liposomes fused with brain metastatic cell and reactive astrocyte membranes (LAsomes) to block gap junctions and attenuate chemoresistance. LAsomes effectively penetrated the blood–brain barrier via semaphorin 4D (SEMA 4D)─Plexin B1 interactions and actively migrated to their source cells via homotypic recognition. Consequently, LAsomes effectively inhibited material transfer and Ca²⁺ flow from metastatic cells to astrocytes via gap junctions, thereby markedly increasing the sensitivity of metastatic tumor cells to chemotherapy. These results reveal that closing the gap junctions may be a promising therapeutic strategy for intractable brain metastasis.

Electrochemical humidity (ECH) sensors that integrate power generation and humidity sensing have attracted great research attention in recent years. However, the design of high-performance ECH sensors faces many challenges. Namely, the working mechanism of the ECH sensors is still controversial, and related self-powered applications have not been well implemented. To overcome these limitations, this study constructs an ECH sensor with high power-generation and humidity-sensing performance using the KCl/carbon black/halloysite nanotubes (KCl/CB/HNTs) as a humidity-sensing electrolyte. The proposed ECH sensor has a wide humidity-sensing response of 10.9%–91.5% relative humidity (RH), and a single ECH sensor can output 1.46 V with a maximum power of 133.2 μW at 91.5% RH. Particularly, the unprecedented mixed chemical reactions at the positive electrode, including the hydrogen evolution reaction and oxygen reduction reaction, are analyzed using multiple characterization and testing techniques. The analysis results provide solid experimental evidence for the current controversial working mechanism of ECH sensors. Due to the advantage of high-power generation, the proposed ECH sensor can be used for self-powered humidity detection. This study provides a valuable reference for improving the power generation of ECH sensors and solid evidence for clarifying their working mechanism, which could be beneficial for guiding the future development of ECH sensors.

The quest for economical and highly efficient nanomaterials for the alkaline hydrogen oxidation reaction (HOR) is imperative in advancing the technology of anion exchange membrane fuel cells (AEMFCs). Efforts using Pt-based electrocatalysts for alkaline HOR are greatly plagued by their finitely intrinsic activities and significant CO poisoning, stemming from the difficulty of simultaneously optimizing surface adsorption toward different hydrogen-related adsorbates. Herein, Ru clusters coupled with Eu₂O₃ immobilized within N-doped carbon nanofibers (Ru/Eu₂O₃@N-CNFs) are developed toward drastically boosted electrocatalysis for HOR via a d-p-f gradient orbital coupling strategy. Theoretical calculations and in situ operando spectroscopy discover that the induction of Eu₂O₃ optimizes the Ru site electronic structure via constructing the gradient orbital coupling of Ru(3d)-O(2p)-Eu(4f), leading to optimal H intermediates, improved adsorption ability of OH and reduced energy barrier of water formation, and promoted CO oxidation, endowing the Ru/Eu₂O₃ as the promising catalyst alternative for fast alkaline hydrogen electrooxidation. As a result, the Ru/Eu₂O₃@N-CNFs reach an impressive kinetic current densities (j_k) value of 156.3 mA cm^–2 at 50 mV (38.4 times higher than Pt/C), and decent stability over 35000 s continuous operation. This comprehensive investigation featuring d-p-f gradient orbital coupling provides valuable insights for the strategic development of high-performance Ru-based materials for HOR and beyond.