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Abstract Highly aligned aggregation state structures have great significance for effective charge‐carrier transport in organic semiconductors. Several methods have been developed to provide organic semiconducting molecules with highly oriented aggregation state structure; among these, using a water surface to form organic semiconductor films is a widely implemented strategy, wherein solutions are spread on the surface of water. However, common techniques of film formation on water surfaces generally result in a nonuniform orientation of the film owing to the isotropic spread process of droplets on the water surface. In this study, a spatially confined air/water interfacial assembly method is proposed to obtain uniformly aligned monolayer and multilayer poly(diketopyrrolopyrrole‐thieno[3,2‐b]thiophene) thin films with controlled thickness. The structural and morphological characterizations obtained using atomic force microscopy, high‐resolution transmission electron microscopy, and grazing incidence wide‐angle X‐ray scattering indicates the crystalline structure of the thin films and high alignment of the molecular chains. The maximum mobility of the thin films reaches up to 2.06 and 0.5 cm2 V−1 s−1 in the parallel and perpendicular direction, respectively, indicating apparent anisotropic electrical properties. Furthermore, an inverter based on these thin films exhibits a voltage gain of up to 70, demonstrating the potential of applying the proposed technique to logic circuits.

α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry. Diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-oxydiazomethylation of alkenes through visible-light photoredox catalysis. This process exploits photocatalyzed strategy to convert alkenes to γ-formyloxyl-α-diazoesters using α-diazo iodonium salts as carbyne precursors, featuring wide substrate tolerance and broad late-stage diversifications. Mechanistic studies suggest that the formation of γ-carbocation-tethered α-diazoesters plays a crucial role in trapping DMF and H2O to allow for this transformation., (© 2024 Wiley‐VCH GmbH.)

Cancer involves tumor cells and tumor-specific immunity. The ability to accurately quantify tumor-specific immunity is limited. Most immunotherapies function by activating new effector tumor antigen-specific T cells (ETASTs) or reactivating the pre-existing ETASTs repertoire. Therefore, the amount of ETASTs can be used to characterize immunotherapy efficacy. Tumor antigens are highly heterogeneous and detecting most ETASTs is challenging. Therefore, nanoparticles loading whole-cell tumor antigens are used to activate and detect pan-clones ETASTs in the blood. The differences between ETASTs and other T cells are transformed into activated and non-activated states. By measuring markers of the activated status and cytotoxic function of ETASTs, it can distinguish ETASTs from other T cells. ETASTs in patients with lung cancer are higher than those in healthy individuals and those with benign pulmonary nodules. Therapeutic efficacy positively correlated with the number of ETASTs in the blood. ETATS levels increase only in the blood of patients who respond to immunotherapy. Single-cell sequencing studies validated these findings. This study provides a highly accurate, specific, non-invasive, and efficient biomarker for predicting immunotherapy efficacy in lung and other cancers. This method can also be applied to evaluate the efficacy of other treatments, such as radiotherapy, oncolytic viruses, and nanomedicine-based therapies., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Emerging diagnostic scenarios, such as population surveillance by pooled testing and on-site rapid diagnosis, highlight the importance of advanced microfluidic systems for in vitro diagnostics. However, the widespread adoption of microfluidic technology faces challenges due to the lack of standardized design paradigms, posing difficulties in managing macro-micro fluidic interfaces, reagent storage, and complex macrofluidic operations. This paper introduces a novel modular-based mesoscopic design paradigm, featuring a core "needle-plug/piston" structure with versatile variants for complex fluidic operations. These structures can be easily coupled with various microfluidic platforms to achieve truly self-contained microsystems. Incorporated into a "3D extensible" design architecture, the mesoscopic design meets the demands of function integration, macrofluid manipulations, and flexible throughputs for point-of-care nucleic acid testing. Using this approach, an ultra-sensitive nucleic acid detection system is developed with a limit of detection of ten copies of SARS-CoV-2 per mL. This system efficiently conducts large-scale pooled testing from 50 pharyngeal swabs in a tube with an uncompromised sensitivity, enabling a truly "sample-in-answer-out" microsystem with exceptional performance., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

The pursuit of sustainable practices through the chemical recycling of polyamide wastes holds significant potential, particularly in enabling the recovery of a range of nitrogen-containing compounds. Herein, we report a novel strategy to upcycle polyamide wastes to tertiary amines with the assistance of H 2 in acetic acid under mild conditions (e.g., 180 °C), which is achieved over anatase TiO 2 supported Mo single atoms and Rh nanoparticles. In this protocol, the polyamide is first converted into diacetamide intermediates via acidolysis, which are subsequently hydrogenated into corresponding carboxylic acid monomers and tertiary amines in 100 % selectivity. It is verified that Mo single atoms and Rh nanoparticles work together to activate both amide bonds of the diacetamide intermediate, and synergistically catalyze its hydrodeoxygenation to form tertiary amine, but this catalyst is ineffective for hydrogenation of carboxylic acid. This work presents an effective way to reconstruct various polyamide wastes into tertiary amines and carboxylic acids, which may have promising application potential., (© 2024 Wiley-VCH GmbH.)

Cold exposure (CE) therapy is an innovative and cost-efficient cancer treatment that activates brown adipose tissue to compete for glucose uptake, leading to metabolic starvation in tumors. Exploring the combined antitumor mechanisms of CE and traditional therapies (such as nanocatalysis) is exciting and promising. In this study, a platelet membrane biomimetic single-atom nanozyme (SAEs) nanodrug (PFB) carrying bis-2-(5-phenylacetamido-1, 2, 4-thiadiazol-2-yl) ethyl sulfide (BPTES) is developed for use in cancer CE therapy. Owing to the platelet membrane modification, PFB can effectively target tumors. Upon entering cancer cells, the dual starvation effect induced by CE treatment and BPTES can significantly diminish intracellular glucose and ATP levels, resulting in a substantial reduction in cellular (glutathione) GSH, which can enhance the cytotoxic efficacy of reactive oxygen species generated by SAEs. This strategy not only boosts ROS production in tumors, but also strengthens immune responses, particularly by increasing memory T-cell abundance and suppressing distant tumor growth and tumor metastasis. Compared with SAEs therapy alone, this combined approach offers superior benefits for tumor immunotherapy. This study achieves a combination of CE and nanomedicines for the first time, providing new ideas for future nanomedicine combination therapy modalities., (© 2024 Wiley‐VCH GmbH.)

The challenges of multi-pathway immune resistance and systemic toxicity caused by the direct injection of immune checkpoint inhibitors are critical factors that compromise the effectiveness of clinical immune checkpoint blockade therapy. In this context, natural polyphenols have been employed as the primary component to construct a targeted and acid-responsive PD-L1 antibody (αPD-L1) delivery nanoplatform. This platform incorporates garcinol, an inhibitor of the Nuclear Factor Kappa-B (NF-κB) signaling pathway, to regulate pro-tumor immune escape cytokines and regulatory T cells. Additionally, the nanoplatform has been verified to induce immunogenic cell death (ICD), which promotes the maturation of dendritic cells and enhances the activity of cytotoxic T lymphocytes. In vivo and in vitro experimental results demonstrated that the nanoplatform can boost the immune response through a PD-L1 and NF-κB blocking/ICD inducing three-pronged strategy, thereby effectively combating tumor growth and metastasis., (© 2024 Wiley‐VCH GmbH.)

Dipeptidyl peptidase 4 (DPP4) positive fibroblasts play a pivotal role in scar development following skin injury. Heterogeneous vascular endothelial cells (ECs) within scarred areas retain the capacity to drive tissue regeneration and repair. Simultaneously, TREM2 macrophages play a crucial role in the progression and resolution of fibrosis by engaging in mutual regulation with ECs. However, effective strategies to inhibit scar formation through multi-factor regulation of the scar microenvironment remain a challenge. Here, CAR-TREM2-macrophages (CAR-TREM2-Ms) capable of targeting DPP4 + fibroblasts and modulating ECs subtype within the scar microenvironment are engineered to effectively prevent scarring. Hydrogel microporous microneedles (mMNs) are employed to deliver CAR-TREM2-Ms, which can effectively alleviate scar. Single-cell transcriptome sequencing (scRNA-seq) analysis reveals that CAR-TREM2-Ms can modify ECs fibrotic phenotype and regulate fibrosis by suppressing the profibrotic gene leucine-rich-alpha-2-glycoprotein 1 (Lrg1). In vitro experiments further demonstrate that CAR-TREM2-Ms improve the scar microenvironment by phagocytosing DPP4 + fibroblasts and suppressing TGFβ secretion. This, in turn, inhibits the phenotypic conversion of LRG1 ECs and provides multifactorial way of alleviating scars. This study uncovers the evidence that mMNs attached to CAR-TREM2-Ms may exert vital influences on skin scarring through the regulation of the skin scar microenvironment, providing a promising approach for treating posttraumatic scarring., (© 2024 Wiley‐VCH GmbH.)

This study pioneers a novel strategy for synthesizing solar-blind ultraviolet (UV) nonlinear optical (NLO) crystals through functional groups sequential construction, effectively addressing the inherent trade-offs among broad transmittance, enhanced second-harmonic generation (SHG), and optimal birefringence. We have developed two innovative van der Waals layered germanous phosphites: GeHPO 3 , the first Ge(II)-based oxide NLO crystal which exhibits a black phosphorus-like structure, and K(GeHPO 3 ) 2 Br, distinguished by its exceptional birefringence and graphene-like structure. Significantly, GeHPO 3 exhibits a remarkable array of NLO properties, including the highest SHG coefficient recorded among all NLO crystals for phase-matching and generating 266 nm coherent light via quadruple frequency conversion. It delivers a potent SHG intensity, surpassing KH 2 PO 4 (KDP) by 10.3 times at 1064 nm and β-BaB 2 O 4 by 1.3 times at 532 nm, complemented by a distinct UV absorption edge at 211 nm and moderate birefringence of 0.062 at 546 nm. Comprehensive theoretical analysis links these exceptional characteristics to the unique NLO-active GeO 3 4- units and the distinctive, highly ordered layered structures. Our findings deliver essential experimental insights into the development of Ge(II)-based optoelectronic materials and present a strategic blueprint for engineering structure-driven functional materials with customized properties., (© 2024 Wiley-VCH GmbH.)

In recent years, cancer immunotherapy has undergone a transformative shift toward personalized and targeted therapeutic strategies. Bacteria-derived outer membrane vesicles (OMVs) have emerged as a promising and adaptable platform for cancer immunotherapy due to their unique properties, including natural immunogenicity and the ability to be engineered for specific therapeutic purposes. In this review, a comprehensive overview is provided of state-of-the-art techniques and methodologies employed in the engineering of versatile OMVs for cancer immunotherapy. Beginning by exploring the biogenesis and composition of OMVs, unveiling their intrinsic immunogenic properties for therapeutic appeal. Subsequently, innovative approaches employed to engineer OMVs are delved into, ranging from the genetic engineering of parent bacteria to the incorporation of functional molecules. The importance of rational design strategies is highlighted to enhance the immunogenicity and specificity of OMVs, allowing tailoring for diverse cancer types. Furthermore, insights into clinical studies and potential challenges utilizing OMVs as cancer vaccines or adjuvants are also provided, offering a comprehensive assessment of the current landscape and future prospects. Overall, this review provides valuable insights for researchers involved in the rapidly evolving field of cancer immunotherapy, offering a roadmap for harnessing the full potential of OMVs as a versatile and adaptable platform for cancer treatment., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Clinical multidrug-resistant Pseudomonas aeruginosa (MDR-PA) is the leading cause of refractory bacterial keratitis (BK). However, the reported BK treatment methods lack biosecurity and bioavailability, which usually causes irreversible visual impairment and even blindness. Herein, for BK caused by clinically isolated MDR-PA infection, armed phages are modularized with the type I photosensitizer (PS) ACR-DMT, and an intelligent phage eyedrop is developed for combined phagotherapy and photodynamic therapy (PDT). These eyedrops maximize the advantages of bacteriophages and ACR-DMT, enabling more robust and specific targeting killing of MDR-PA under low oxygen-dependence, penetrating and disrupting biofilms, and efficiently preventing biofilm reformation. Altering the biofilm and immune microenvironments alleviates inflammation noninvasively, promotes corneal healing without scar formation, protects ocular tissues, restores visual function, and prevents long-term discomfort and pain. This strategy exhibits strong scalability, enables at-home treatment of ocular surface infections with great patient compliance and a favorable prognosis, and has significant potential for clinical application., (© 2024 Wiley‐VCH GmbH.)

Excited-state intramolecular proton transfer (ESIPT) has attracted great attention in fluorescent sensors and luminescent materials due to its unique photobiological and photochemical features. However, the current structures are far from meeting the specific demands for ESIPT molecules in different scenarios; the try-and-error development method is labor-intensive and costly. Therefore, it is imperative to devise novel approaches for the exploration of promising ESIPT fluorophores. This research proposes an artificial intelligence approach aiming at exploring ESIPT molecules efficiently. The first high-quality ESIPT dataset and a multi-level prediction system are constructed that realized accurate identification of ESIPT molecules from a large number of compounds under a stepwise distinguishing from conventional molecules to fluorescent molecules and then to ESIPT molecules. Furthermore, key structural features that contributed to ESIPT are revealed by using the SHapley Additive exPlanations (SHAP) method. Then three strategies are proposed to ensure the ESIPT process while keeping good safety, pharmacokinetic properties, and novel structures. With these strategies, >700 previously unreported ESIPT molecules are screened from a large pool of 570 000 compounds. The ESIPT process and biosafety of optimal molecules are successfully validated by quantitative calculation and experiment. This novel approach is expected to bring a new paradigm for exploring ideal ESIPT molecules., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Photodynamic therapy (PDT) is a promising cancer treatment, but limited oxygen supply in tumors (hypoxia) can hinder its effectiveness. This is because traditional PDT relies on Type-II reactions that require oxygen. Type-I photosensitizers (PSs) offer a promising approach to overcome the limitations of tumor photodynamic therapy (PDT) in hypoxic environments. To leverage the advantages of Type-I PDT, the design and evaluation of a series of Type-I PSs for developing pure Type-1 PSs, by incorporating benzene, thiophene, or bithiophene into the donor-acceptor molecular skeleton are reported. Among them, CTTI (with bithiophene) shows the best performance, generating the most superoxide radical (O 2 •- ) upon light irradiation. Importantly, CTTI exclusively produced superoxide radicals, avoiding the less effective Type-II pathway. This efficiency is due to CTTI's energy gap and low reduction potential, which favor electron transfer to oxygen for O 2 •- generation. Finally, CTTI NPs are successfully fabricated by encapsulating CTTI into liposomes, and validated to be effective in killing tumor cells, even under hypoxic conditions, making them promising hypoxia-tolerant tumor phototheranostic agents in both in vitro and in vivo applications., (© 2024 Wiley‐VCH GmbH.)

While the formation of an inorganic-rich solid electrolyte interphase (SEI) plays a crucial role, the persistent challenge lies in the formation of an organic-rich SEI due to the high solvent ratio in low-concentration electrolytes (LCEs), which hinders the achievement of high-performance lithium metal batteries. Herein, by incorporating di-fluoroethylene carbonate (DFEC) as a non-solvating cosolvent, a solvation structure dominated by anions is introduced in the innovative LCE, leading to the creation of a durable and stable inorganic-rich SEI. Leveraging this electrolyte design, the Li||NCM83 cell demonstrates exceptional cycling stability, maintaining 82.85% of its capacity over 500 cycles at 1 C. Additionally, Li||NCM83 cell with a low N/P ratio (≈2.57) and reduced electrolyte volume (30 µL) retain 87.58% of its capacity after 150 cycles at 0.5 C. Direct molecular information is utilized to reveal a strong correlation between solvation structures and reduction sequences, proving the anion-dominate solvation structure can impedes the preferential reduction of solvents and constructs an inorganic-rich SEI. These findings shed light on the pivotal role of solvation structures in dictating SEI composition and battery performance, offering valuable insights for the design of advanced electrolytes for next-generation lithium metal batteries., (© 2024 Wiley‐VCH GmbH.)

New adjuvants that trigger cellular immune responses are urgently needed for the effective development of cancer and virus vaccines. Motivated by recent discoveries that show activation of type I interferon (IFN-I) signaling boosts T cell immunity, this study proposes that targeting this pathway can be a strategic approach to identify novel vaccine adjuvants. Consequently, a comprehensive chemical screening of 6,800 small molecules is performed, which results in the discovery of the natural compound picrasidine S (PS) as an IFN-I inducer. Further analysis reveals that PS acts as a powerful adjuvant, significantly enhancing both humoral and cellular immune responses. At the molecular level, PS initiates the activation of the cGAS-IFN-I pathway, leading to an enhanced T cell response. PS vaccination notably increases the population of CD8+ central memory (T CM )-like cells and boosts the CD8+ T cell-mediated anti-tumor immune response. Thus, this study identifies PS as a promising candidate for developing vaccine adjuvants in cancer prevention., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Recently, aqueous zinc ion batteries (AZIBs) with the superior theoretical capacity, high safety, low prices, and environmental protection, have emerged as a contender for advanced energy storage. However, challenges related to cathode materials, such as dissolution, instability, and structural collapse, have hindered the progress of AZIBs. Here, a novel AZIB is constructed using an oxidized 2D layered MnBi 2 Te 4 cathode for the first time. The oxidized MnBi 2 Te 4 cathode with large interlayer spacing and low energy barrier for zinc ion diffusion at 240 °C, exhibited impressive characteristics, including a high reversibility capacity of 393.1 mAh g -1 (0.4 A g -1 ), outstanding rate performance, and long cycle stability. Moreover, the corresponding aqueous button cell also exhibits excellent electrochemical performance. To demonstrate the application in practice in the realm of flexible wearable electronics, a quasi-solid-state micro ZIB (MZIB) is constructed and shows excellent flexibility and high-temperature stability (the capacity does not significantly degrade when the temperature reaches 100 °C and the bending angle exceeds 150°). This research offers effective tactics for creating high-performance cathode materials for AZIBs., (© 2024 Wiley‐VCH GmbH.)

A novel Fe 2 Mo 3 O 8 /MoO 2 @MoS 2 nanocomposite is synthesized for extremely sensitive detection of NH 3 in the breath of kidney disease patients at room temperature. Compared to MoS 2 , α-Fe 2 O 3 /MoS 2 , and MoO 2 @MoS 2 , it shows the optimal gas-sensing performance by optimizing the formation of Fe 2 Mo 3 O 8 at 900 °C. The annealed Fe 2 Mo 3 O 8 /MoO 2 @MoS 2 nanocomposite (Fe 2 Mo 3 O 8 /MoO 2 @MoS 2 -900 °C) sensor demonstrates a remarkably high selectivity of NH 3 with a response of 875% to 30 ppm NH 3 and an ultralow detection limit of 3.7 ppb. This sensor demonstrates excellent linearity, repeatability, and long-term stability. Furthermore, it effectively differentiates between patients at varying stages of kidney disease through quantitative NH 3 measurements. The sensing mechanism is elucidated through the analysis of alterations in X-ray photoelectron spectroscopy (XPS) signals, which is supported by density functional theory (DFT) calculations illustrating the NH 3 adsorption and oxidation pathways and their effects on charge transfer, resulting in the conductivity change as the sensing signal. The excellent performance is mainly attributed to the heterojunction among MoS 2 , MoO 2 , and Fe 2 Mo 3 O 8 and the exceptional adsorption and catalytic activity of Fe 2 Mo 3 O 8 /MoO 2 @MoS 2 -900 °C for NH 3 . This research presents a promising new material optimized for detecting NH 3 in exhaled breath and a new strategy for the early diagnosis and management of kidney disease., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Utilizing the ionic flux to generate voltage output has been confirmed as an effective way to meet the requirements of clean energy sources. Different from ionic thermoelectric (i-TE) and hydrovoltaic devices, a new hydrothermal chemical generator is designed by amorphous FeCl 3 particles dispersing in MWCNT and unique ferric chloride or water gate. In the presence of gate, the special ion behaviors enable the cell to present a constant voltage of 0.60 V lasting for over 96 h without temperature difference. Combining the differences of cation concentration, humidity and temperature between the right and left side of sample, the maximum short-circuit current and power output can be obtained to 168.46 µA and 28.11 µW, respectively. The generator also can utilize the low-grade heat to produce electricity wherein Seebeck coefficient is 6.79 mV K -1 . The emerged hydrothermal chemical generator offers a novel approach to utilize the low-grade heat, water and salt solution resources, which provides a simple, sustainable and low-cost strategy to realize energy supply., (© 2024 Wiley‐VCH GmbH.)

Critical-size bone defects pose a formidable challenge in clinical treatment, prompting extensive research efforts to address this problem. In this study, an inorganic-organic multifunctional composite hydrogel denoted as PLG-g-TA/VEGF/Sr-BGNPs is developed, engineered for the synergistic management of bone defects. The composite hydrogel demonstrated the capacity for mineralization, hydroxyapatite formation, and gradual release of essential functional ions and vascular endothelial growth factor (VEGF) and also maintained an alkaline microenvironment. The composite hydrogel promoted the proliferation and osteogenic differentiation of rat bone marrow mesenchymal stem cells (rBMSCs), as indicated by increased expression of osteogenesis-related genes and proteins in vitro. Moreover, the composite hydrogel significantly enhanced the tube-forming capability of human umbilical vein endothelial cells (HUVECs) and effectively inhibited the process of osteoblastic differentiation of nuclear factor kappa-B ligand (RANKL)-induced Raw264.7 cells and osteoclast bone resorption. After the implantation of the composite hydrogel into rat cranial bone defects, the expression of osteogenic and angiogenic biomarkers increased, substantiating its efficacy in promoting bone defect repair in vivo. The commendable attributes of the multifunctional composite hydrogel underscore its pivotal role in expediting hydrogel-associated bone growth and repairing critical bone defects, positioning it as a promising adjuvant therapy candidate for large-segment bone defects., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Ratiometric afterglow luminescent (AGL) probes are attractive for in vivo imaging due to their high sensitivity and signal self-calibration function. However, there are currently few ratiometric AGL probes available for imaging enzymatic activity in living organisms. Here, we present an energy diversion (ED) strategy that enables the design of an enzyme-activated ratiometric AGL probe (RAG-RGD) for in vivo afterglow imaging. The ED process provides RAG-RGD with a radiative transition for an 'always on' 520-nm AGL signal (AGL 520 ) and a cascade three-step energy transfer (ET) process for an 'off-on' 710-nm AGL signal (AGL 710 ) in response to a specific enzyme. Using matrix metalloproteinase-2 (MMP-2) as an example, RAG-RGD shows a significant ~11-fold increase in AGL 710 /AGL 520 toward MMP-2. This can sensitively detect U87MG brain tumors through ratiometric afterglow imaging of MMP-2 activity, with a high signal-to-background ratio and deep imaging depth. Furthermore, by utilizing the self-calibration effect of ratiometric imaging, RAG-RGD demonstrated a strong negative correlation between the AGL 710 /AGL 520 value and the size of orthotopic U87MG tumor, enabling accurate monitoring of orthotopic glioma growth in vivo. This ED process may be applied for the design of other enzyme-activated ratiometric afterglow probes for sensitive afterglow imaging., (© 2024 Wiley-VCH GmbH.)

Ferroptosis is an emerging non-apoptotic death process, mainly involving lipid peroxidation (LPO) caused by iron accumulation, which is potentially lethal to the intrinsically apoptotic-resistant malignant tumor. However, it is still restricted by the inherent antioxidant systems of tumor cells and the poor efficacy of traditional iron-based ferroptosis initiators. Herein, the study develops a novel ferroptosis-inducing agent based on PEGylated Cu + /Cu 2+ -doped black phosphorus@polypyrrole heterojunction (BP@CPP), which is constructed by utilizing the phosphate on the surface of BP to chelate Cu ions and initiating subsequent in situ polymerization of pyrrole. As a novel Z-scheme heterojunction, BP@CPP possesses an excellent photocatalytic activity in which the separated electron-hole pairs under laser irradiation endow it with powerful oxidizing and reducing capacities, which synergy with Cu + /Cu 2+ self-cycling catalyzing Fenton-like reaction to further strengthen reactive oxygen species (ROS) accumulation, glutathione (GSH) depletion, and glutathione peroxidase 4 (GPX4) inactivation, ultimately leading to efficient ferroptosis. Systematic in vitro and in vivo evaluations demonstrate that BP@CPP effectively inhibit tumor growth by inducing desired ferroptosis while maintaining a favorable biosafety in the body. Therefore, the developed BP@CPP-based ferroptosis initiator provides a promising strategy for ferroptosis-like cancer therapy., (© 2023 Wiley‐VCH GmbH.)

Peripheral nerve block is performed for precise pain control and lesser side effects after surgery by reducing opioid consumption. Injectable hydrogel delivery systems with high biosafety and moisture content have good clinical application prospects for local anesthetic delivery. However, how to achieve high drug loading and long-term controlled release of water-soluble narcotic drugs remains a big challenge. In this study, heterogeneous microspheres and an injectable gel-matrix composite drug delivery system are designed in two steps. First, heterogeneous hydrogel microspheres loaded with ropivacaine (HMS-ROP) are prepared using a microfluidic chip and in situ alkalization. An injectable self-healing hydrogel matrix (Gel) is then prepared from modified carboxymethylcellulose (CMC-ADH) and oxidized hyaluronic acid (OHA). A local anesthetic delivery system, Gel/HMS-ROP/dexmedetomidine (DEX), with long-term retention and drug release in vivo is prepared by combining HMS-ROP and Gel/DEX. The drug loading of HMS-ROP reached 41.1%, with a drug release time of over 160 h in vitro, and sensory and motor blockade times in vivo of 48 and 36 h, respectively. In summary, the sequential release and synergistic analgesic effects of the two anesthetics are realized using core-shell microspheres, DEX, and an injectable gel, providing a promising strategy for long-acting postoperative pain management., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Structural and physiological cues provide guidance for the directional migration and spatial organization of endogenous cells. Here, a microchannel scaffold with instructive niches is developed using a circumferential freeze-casting technique with an alkaline salting-out strategy. Thereinto, polydopamine-coated nano-hydroxyapatite is employed as a functional inorganic linker to participate in the entanglement and crystallization of chitosan molecules. This scaffold orchestrates the advantage of an oriented porous structure for rapid cell infiltration and satisfactory immunomodulatory capacity to promote stem cell recruitment, retention, and subsequent osteogenic differentiation. Transcriptomic analysis as well as its in vitro and in vivo verification demonstrates that essential colony-stimulating factor-1 (CSF-1) factor is induced by this scaffold, and effectively bound to the target colony-stimulating factor-1 receptor (CSF-1R) on the macrophage surface to activate the M2 phenotype, achieving substantial endogenous bone regeneration. This strategy provides a simple and efficient approach for engineering inducible bone regenerative biomaterials., (© 2024 Wiley‐VCH GmbH.)

Nanomedicine has reshaped the landscape of cancer treatment. However, its efficacy is still hampered by innate tumor defense systems that rely on adenosine triphosphate (ATP) for fuel, including damage repair, apoptosis resistance, and immune evasion. Inspired by the naturally enzymatic reaction of glucose oxidase (GOx) with glucose, here a novel "two birds with one stone" technique for amplifying enzyme-mediated tumor apoptosis and enzyme-promoted metabolic clearance is proposed and achieved using GOx-functionalized rhenium nanoclusters-doped polypyrrole (Re@ReP-G). Re@ReP-G reduces ATP production while increasing H 2 O 2 concentrations in the tumor microenvironment through GOx-induced enzymatic oxidation, which in turn results in the downregulation of defense (HSP70 and HSP90) and anti-apoptotic Bcl-2 proteins, the upregulation of pro-apoptotic Bax, and the release of cytochrome c. These processes are further facilitated by laser-induced hyperthermia effect, ultimately leading to severe tumor apoptosis. As an enzymatic byproduct, H 2 O 2 catalyzes the conversion of rhenium nanoclusters in Re@ReP-G nanostructures into rhenate from the outside in, which accelerates their metabolic clearance in vivo. This Re@ReP-G-based "two birds with one stone" therapeutic strategy provides an effective tool for amplifying tumor apoptosis and safe metabolic mechanisms., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Basal-like breast cancer (BLBC) is the most aggressive molecular subtype of breast cancer with worse prognosis and fewer treatment options. The underlying mechanisms upon BLBC transcriptional dysregulation and its upstream transcription factors (TFs) remain unclear. Here, among the hyperactive candidate TFs of BLBC identified by bioinformatic analysis, POU4F1 is uniquely upregulated in BLBC and is associated with poor prognosis. POU4F1 is necessary for the tumor growth and malignant phenotypes of BLBC through regulating G1/S transition by direct binding at the promoter of CDK2 and CCND1. More importantly, POU4F1 maintains BLBC identity by repressing ERα expression through CDK2-mediated EZH2 phosphorylation and subsequent H3K27me3 modification in ESR1 promoter. Knocking out POU4F1 in BLBC cells reactivates functional ERα expression, rendering BLBC sensitive to tamoxifen treatment. In-depth epigenetic analysis reveals that the subtype-specific re-configuration and activation of the bivalent chromatin in the POU4F1 promoter contributes to its unique expression in BLBC, which is maintained by DNA demethylase TET1. Together, these results reveal a subtype-specific epigenetically activated TF with critical role in promoting and maintaining BLBC, suggesting that POU4F1 is a potential therapeutic target for BLBC., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Covalent organic frameworks (COFs) are porous organic materials with well-defined and uniform structure. The material is an excellent candidate as a solid adsorbent for iodine adsorption. In the present study, we report the synthesis of COF with porphyrin moiety, TF-TA-COF, by solvothermal reaction, which was characterized by XRD, solid-state 13 C NMR, IR, TGA, and nitrogen adsorption-desorption analysis. TF-TA-COF showed a high specific surface area of 443 m 2  g -1 , and exhibited good adsorption performance for iodine vapor, with an adsorption capacity of 2.74 g g -1 . XPS and Raman spectrum indicated that a hybrid of physisorption and chemisorption took place between host COF and iodine molecules. The electric properties of iodine-loaded TF-TA-COF were also studied. After doped with iodine, the conductivity of the material increased by more than 5 orders of magnitude. The photoconductivity of I 2 -doped COF was also studied and TF-TA-COF showed doping-enhanced photocurrent generation., (© 2023 Wiley-VCH GmbH.)

Induction of pyroptosis can promote anti-PD-L1 therapeutic efficacy due to the release of pro-inflammatory cytokines, but current approaches can cause off target toxicity. Herein, a phthalocyanine-conjugated mesoporous silicate nanoparticle (PMSN) is designed for amplifying sonodynamic therapy (SDT) to augment oxidative stress and induce robust pyroptosis in tumors. The sub-10 nm diameter structure and c(RGDyC)-PEGylated modification enhance tumor targeting and renal clearance. The unique porous architecture of PMSN doubles ROS yield and enhances pyroptotic cell populations in tumors (25.0%) via a cavitation effect. PMSN-mediated SDT treatment efficiently reduces tumor mass and suppressed residual tumors in treated and distant sites by synergizing with PD-L1 blockade (85.93% and 77.09%, respectively). Furthermore, loading the chemotherapeutic, doxorubicin, into PMSN intensifies SDT-pyroptotic effects and increased efficacy. This is the first report of the use of SDT regimens to induce pyroptosis in liver cancer. This noninvasive and effective strategy has potential for clinical translation., (© 2023 Wiley-VCH GmbH.)

2D perovskites have attracted tremendous attention due to their superior optoelectronic properties and potential applications in optoelectronic devices. Especially, the larger bandgap of 2D perovskite means that they are suitable for UV photodetection. However, the layered structure of 2D perovskites hinders the interlayer carrier transport, which limits the improvement of device performance. Therefore, nanoscale structures are normally used to enhance the light absorption ability, which is an effective strategy to improve the photocurrent in 2D perovskite-based photodetectors. Herein, a template-assisted low-temperature method is proposed to fabricate 2D perovskite ((C 6 H 5 C 2 H 4 NH 3 ) 2 PbBr 4 , (PEA) 2 PbBr 4 ) grating single crystal films (GSCFs). The crystallinity of the (PEA) 2 PbBr 4 GSCFs is significantly improved due to the slow evaporation of the precursor solution under low temperatures. Based on this high crystalline quality and extremely ordered microstructures, the metal-semiconductor-metal photodetectors are assembled. Finite-different time-domain (FDTD) simulation and experiment indicate that the GSCF-based photodetectors exhibit significantly improved performance in comparison with the plane devices. The optimized 2D perovskite photodetectors are sensitive to UV light and demonstrate a responsivity and detectivity of 28.6 mA W -1 and 2.4 × 10 11 Jones, respectively. Interestingly, the photocurrent of this photodetector varies as the angle of the incident polarized light, resulting in a high polarization ratio of 1.12., (© 2023 Wiley‐VCH GmbH.)

Based on the pathological characteristics of rheumatoid arthritis, including the overproduction of reactive oxygen species (ROS), inflammatory responses, and osteoclast differentiation, a biomimetic multifunctional nanomedicine (M-M@I) is designed. Iguratimod (IGU) is loaded, which inhibits inflammatory responses and osteoclast differentiation, into mesoporous polydopamine (MPDA), which scavenges ROS. Subsequently, the nanoparticles are coated with a cell membrane of macrophages to achieve actively targeted delivery of the nanoparticles to inflamed joints. It is shown that the M-M@I nanoparticles are taken up well by lipopolysaccharide-induced RAW 264.7 macrophages or bone marrow-derived macrophages (BMDMs). In vitro, the M-M@I nanoparticles effectively scavenge ROS, downregulate genes related to inflammation promotion and osteoclast differentiation, and reduce the proinflammatory cytokines and osteoclast-related enzymes. They also reduce the polarization of macrophages to a pro-inflammatory M1 phenotype and inhibit differentiation into osteoclasts. In mice with collagen-induced arthritis, the M-M@I nanoparticles accumulate at arthritic sites and circulate longer, significantly mitigating arthritis symptoms and bone destruction. These results suggest that the pathology-specific biomimetic multifunctional nanoparticles are effective against rheumatoid arthritis, and they validate the approach of developing multifunctional therapies that target various pathological processes simultaneously., (© 2023 Wiley-VCH GmbH.)

Li-rich layered oxides (LLOs) are among the most promising cathode materials with high theoretical specific capacity (>250 mAh g -1 ). However, capacity decay and voltage hysteresis due tostructural degradation during cycling impede the commercial application of LLOs. Surface engineering and element doping are two methods widely applied tomitigate the structural degradation. Here, it is found that trace amount lanthanide element Yb doping can spontaneously form a surficial Yb-rich layer with high density of oxygen vacancy on the LLO-0.3% Yb (Li 1.2 Mn 0.54 Co 0.13-x Yb x Ni 0.13 O 2 where x = 0.003) cathodes, which mitigating lattice oxygen loss and the non-preferred layered-to-spinel-to-rock salt tri-phase transition. Meanwhile, there are also some Yb ions doped into the lattice of LLO, which enhance the binding energy with oxygen and stabilize the lattice in grain interior during cycling. The dual effects of Yb doping greatly mitigate the structure degradation during cycling, and facilitate fast diffusion of lithium ions. As a result, the LLO-0.3% Yb sample achieves significantly improved cycling stability, with a capacity retention of 84.69% after 100 cycles at 0.2 C and 84.3% after 200 cycles at 1 C. These finding shighlight the promising rare element doping strategy that can have both surface engineering and doping effects in preparing LLO cathodes with high stability., (© 2023 Wiley-VCH GmbH.)

As a common cause of shoulder pain, rotator cuff tears (RCTs) are difficult to treat clinically because of their unsatisfactory prognosis due to the fatty infiltration caused by muscle-derived stem cells (MDSCs). Previous studies have found that rapamycin (RAPA) can inhibit fatty infiltration. However, systemic administration of RAPA may cause complications such as infection and nausea, while local administration of RAPA may lead to the cytotoxicity of tendon cells, affecting the healing of rotator cuffs. In this study, biocompatible and clinically approved polycaprolactone-polyethylene glycol (PCL-PEG) is formulated into an injectable nanoparticle for the sustained release of RAPA. The results indicate that the RAPA/PCL-PEG nanoparticles (NPs) can efficiently prolong the release of RAPA and significantly reduce the cytotoxicity of tendon cells caused by RAPA. The study of the fatty infiltration model in rats with delayed rotator cuff repair shows that weekly intraarticular injection of RAPA/PCL-PEG NPs can more effectively reduce the fatty infiltration and muscle atrophy of rat rotator cuffs and leads to better mechanical properties and gait improvements than a daily intraarticular injection of RAPA. These findings imply that local injection of RAPA/PCL-PEG NPs in the shoulder joints can be a potential clinical option for RCTs patients with fatty infiltration., (© 2023 Wiley-VCH GmbH.)

Sympathetic innervation plays a crucial role in maintaining energy balance and contributes to metabolic pathophysiology. Recent evidence has begun to uncover the innervation landscape of sympathetic projections and sheds light on their important functions in metabolic activities. Additionally, the immune system has long been studied for its essential roles in metabolic health and diseases. In this review, the aim is to provide an overview of the current research progress on the sympathetic regulation of key metabolic organs, including the pancreas, liver, intestine, and adipose tissues. In particular, efforts are made to highlight the critical roles of the peripheral nervous system and its potential interplay with immune components. Overall, it is hoped to underscore the importance of studying metabolic organs from a comprehensive and interconnected perspective, which will provide valuable insights into the complex mechanisms underlying metabolic regulation and may lead to novel therapeutic strategies for metabolic diseases., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

We report here a tumor-pretargted theranostic approach for multimodality imaging-guided synergistic cancer PDT by cascade alkaline phosphatase (ALP)-mediated in situ self-assembly and bioorthogonal inverse electron demand Diels-Alder (IEDDA) reaction. Using the enzymatic catalysis of ALP that continuously catalyses the dephosphorylation and self-assembly of trans-cyclooctene (TCO)-bearing P-FFGd-TCO, a high density of fluorescent and magnetic TCO-containing nanoparticles (FMNPs-TCO) can be synthesized and retained on the membrane of tumor cells. They can act as 'artificial antigens' amenable to concurrently capture lately administrated tetrazine (Tz)-decorated PS (775NP-Tz) and carbonic anhydrase (CA) inhibitor (SA-Tz) via the fast IEDDA reaction. This two-step pretargeting process can further induce FMNPs-TCO regrowth into microparticles (FMNPs-775/SA) directly on tumor cell membranes, which is analyzed by bio-SEM and fluorescence imaging. Thus, efficient enrichment of both SA-Tz and 775NP-Tz in tumors can be achieved, allowing to alleviate hypoxia by continuously inhibiting CA activity and improving PDT of tumors. Findings show that subcutaneous HeLa tumors could be completely eradicated and no tumor recurred after irradiation with an 808 nm laser (0.33 W cm -2 , 10 min). This pretargeted approach may be applied to enrich other therapeutic agents in tumors to improve targeted therapy., (© 2023 Wiley-VCH GmbH.)

Li-CO 2 batteries arouse great interest in the context of carbon neutralization, but their practicability is severely hindered by the sluggish CO 2 redox reaction kinetics at the cathode, which brings about formidable challenges such as high overpotential and low Coulombic efficiency. For the complex multi-electron transfer process, the design of catalysts at the molecular or atomic level and the understanding of the relationship between electron state and performance are essential for the CO 2 redox. However, little attention is paid to it. In this work, using Co 3 S 4 as a model system, density functional theory (DFT) calculations reveal that the adjusted d-band and p-band centers of Co 3 S 4 with the introduction of Cu and sulfur vacancies are hybridized between CO 2 and Li species, respectively, which is conducive to the adsorption of reactants and the decomposition of Li 2 CO 3 , and the experimental results further verify the effectiveness of energy band engineering. As a result, a highly efficient bidirectional catalyst is produced and shows an ultra-small voltage gap of 0.73 V and marvelous Coulombic efficiency of 92.6%, surpassing those of previous catalysts under similar conditions. This work presents an effective catalyst design and affords new insight into the high-performance cathode catalyst materials for Li-CO 2 batteries., (© 2023 Wiley-VCH GmbH.)

Singlet fission is a phenomenon that could significantly improve the efficiency of photovoltaic devices. Indolonaphthyridine thiophene (INDT) is a photostable singlet fission material that could potentially be utilised in singlet fission-based photovoltaic devices. This study investigates the intramolecular singlet fission (i-SF) mechanism of INDT dimers linked via para-phenyl, meta-phenyl and fluorene bridging groups. Using ultra-fast spectroscopy the highest rate of singlet fission is found in the para-phenyl linked dimer. Quantum calculations show the para-phenyl linker encourages enhanced monomer electronic coupling. Increased rates of singlet fission were also observed in the higher polarity o-dichlorobenzene, relative to toluene, indicating that charge-transfer states have a role in mediating the process. The mechanistic picture of polarisable singlet fission materials, such as INDT, extends beyond the traditional mechanistic landscape., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Metal oxide gas sensors have long faced the challenge of low response and poor selectivity, especially at room temperature (RT). Herein, a synergistic effect of electron scattering and space charge transfer is proposed to comprehensively improve gas sensing performance of n-type metal oxides toward oxidizing NO 2 (electron acceptor) at RT. To this end, the porous SnO 2 nanoparticles (NPs) assembled from grains of about 4 nm with rich oxygen vacancies are developed through an acetylacetone-assisted solvent evaporation approach combined with precise N 2 and air calcinations. The results show that the as-fabricated porous SnO 2 NPs sensor exhibits an unprecedented NO 2 -sensing performance, including outstanding response (R g /R a  = 772.33 @ 5 ppm), fast recovery (<2 s), an extremely low detection limit (10 ppb), and exceptional selectivity (response ratio >30) at RT. Theoretical calculation and experimental tests confirm that the excellent NO 2 sensing performance is mainly attributed to the unique synergistic effect of electron scattering and space charge transfer. This work proposes a useful strategy for developing high-performance RT NO 2 sensors using metal oxides, and provides an in-depth understanding for the basic characteristics of the synergistic effect on gas sensing, paving the way for efficient and low power consumption gas detection at RT., (© 2023 Wiley-VCH GmbH.)

Solid-state ionic conductive elastomers (ICEs) can fundamentally overcome the disadvantages of hydrogels and ionogels (their liquid components tend to leak or evaporate), and are considered to be ideal materials for flexible ionic sensors. In this study, a liquid-free ionic polyurethane (PU) type conductive elastomer (ICE-2) was synthesized and studied. The PU type matrix with microphase separation endowed ICE-2 with excellent mechanical versatility. The disulfide bond exchange reaction in the hard phase and intermolecular hydrogen bonds contributed to damage repairing ability. ICE-2 exhibited good ionic conductivity (2.86×10 -6  S/cm), high transparency (average transmittance >89 %, 400~800 nm), excellent mechanical properties (tensile strength of 3.06 MPa, elongation at break of 1760 %, and fracture energy of 14.98 kJ/m 2 ), appreciable self-healing ability (healing efficiency >90 %), satisfactory environmental stability, and outstanding recyclability. The sensor constructed by ICE-2 could not only realize the perception of temperature changes, but also accurately and sensitively detect various human activities, including joint movements and micro-expression changes. This study provides a simple and effective strategy for the development of flexible and soft ionic conductors for sensors and human-machine interfaces., (© 2023 Wiley-VCH GmbH.)

The main obstacle of ionic thermo-electrochemical cells (TECs) in continuous power supply lies in a low heat-to-electricity energy conversion efficiency because most TECs work in thermodiffusion mode in which the ions are confined in a liquid/electrolyte media. The introduction of the redox couple onto the electrode surface may overcome the obstacle by resolving the low mass transport rate of ions caused by the redox process occurring near but not on the electrode surface. Herein, the authors demonstrate enhancement of TECs by integrating the redox couple directly onto the electrode surface to maximize the mass transport efficiency. A discontinuous interfacial modification strategy is developed by using a carbon cloth/iron (II/III) phytate as the symmetric electrodes. The gelled electrolyte consisting of a polyacrylamide matrix and phytic acid is shown to promote selective ion diffusion. A synergistic combination consisting of the thermodiffusion effect and redox reactions on the electrode is established in a pre-treated layout. Such TEC affords a high output voltage of 0.4 V, an excellent instantaneous output power density (20.26 mW m -2 K -2 ) and a record-high 2 h output energy density (2451 J m -2 ) under T H = 30 °C with T C = 15 °C, with an ultrahigh Carnot-relative efficiency of 1.12%., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Mesenchymal stem cell (MSC) therapies have been brought forward as a promising treatment modality for cutaneous wound healing. However, current approaches for stem cell delivery have many drawbacks, such as lack of targetability and cell loss, leading to poor efficacy of stem cell therapy. To overcome these problems, in the present study, an in situ cell electrospinning system is developed as an attractive approach for stem cell delivery. MSCs have a high cell viability of over 90% even with a high applied voltage of 15 kV post-cell electrospinning process. In addition, cell electrospinning does not show any negative effect on the surface marker expression and differentiation capacity of MSCs. In vivo studies demonstrate that in situ cell electrospinning treatment can promote cutaneous wound healing through direct deposition of bioactive fish gelatin fibers and MSCs onto wound sites, leading to a synergic therapeutic effect. The approach enhances extracellular matrix remodeling by increasing collagen deposition, promotes angiogenesis by increasing the expression of vascular endothelial growth factor (VEGF) and forming small blood vessels, and dramatically reduces the expression of interleukin-6 (IL-6) during wound healing. The use of in situ cell electrospinning system potentially provides a rapid, no touch, personalized treatment for cutaneous wound healing., (© 2023 Wiley-VCH GmbH.)

Higher amines are important high-valuable chemicals with wide applications, and amination of alcohols is a green route to them, which however generally suffers from harsh reaction conditions and use of equivalent base. Herein, we report an ionic-liquid (IL) hydrogen-bonding promoted dihydrogen autotransfer strategy for amination of alcohols to higher amines over cobalt catalyst under base-free conditions. Co(BF 4 ) 2  ⋅ 6 H 2 O complexed with triphos and IL (e. g., tetrabutylphosphonium tetrafluoroborate, [P 4444 ][BF 4 ]) shows high performances for the reaction and is tolerant of a wide scope of amines and alcohols, affording higher amines in good to excellent yields. Mechanism investigation indicates that the [BF 4 ] - anion activates the alcohol via hydrogen bonding, promoting transfer of both hydroxyl H and α-H atoms of alcohol to the cobalt catalyst to form an aldehyde intermediate and cobalt dihydride complex, which are involved in the subsequent reductive amination. This strategy provides a green and effective route for alcohol amination, which may have promising applications in alcohol-involved alkylation reactions., (© 2023 Wiley-VCH GmbH.)

Proteins are ubiquitously modified with glycans of varied chemical structures through distinct glycosidic linkages, making the landscape of protein glycosylation challenging to map. Profiling of intact glycopeptides with mass spectrometry (MS) has recently emerged as a powerful tool for revealing matched information of the glycosylation sites and attached glycans (i.e., intact glycosites), but is largely limited to individual glycosylation types. Herein, we describe Click-iG, which integrates metabolic labeling of glycans with clickable unnatural sugars, an optimized MS method, and a tailored version of pGlyco3 software to enable simultaneous enrichment and profiling of three types of intact glycopeptides: N-linked, mucin-type O-linked, and O-GlcNAcylated glycopeptides. We demonstrate the utility of Click-iG by the identification of thousands of intact glycosites in cell lines and living mice. From the mouse lung, heart, and spleen, a total of 2053 intact N-glycosites, 262 intact O-GalNAc glycosites, and 1947 O-GlcNAcylation sites were identified. Click-iG-enabled comprehensive coverage of the protein glycosylation landscape lays the foundation for interrogating crosstalk between different glycosylation pathways., (© 2023 Wiley-VCH GmbH.)

Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P 2 nanosheet bifunctional catalyst (Ru-Ni(Fe)P 2 /NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P 2 , and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P 2 /NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm -2 for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO 2 /NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm -2 and 600 mA cm -2 for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting., (© 2023 Wiley-VCH GmbH.)

Small-diameter tissue-engineered vascular grafts (sdTEVGs) are essential materials used in bypass or replacement surgery for cardiovascular diseases; however, their application efficacy is limited because of patency rates, especially under hyperlipidemia, which is also clinically observed in patients with cardiovascular diseases. In such cases, improving sdTEVG patency is challenging because cholesterol crystals easily cause thrombosis and impede endothelialization. Herein, the development of a biomimetic antithrombotic sdTEVG incorporating cholesterol oxidase and arginine into biomineralized collagen-gold hydrogels on a sdTEVG surface is described. Biomimetic antithrombotic sdTEVGs represent a multifunctional substrate for the green utilization of hazardous substances and can convert cholesterol into hydrogen peroxide, which can react with arginine to generate nitric oxide (NO). NO is a vasodilator that can simulate the antithrombotic action of endothelial cells under hyperlipidemic conditions. In vivo studies show that sdTEVGs can rapidly produce large amounts of NO via a cholesterol catalytic cascade to inhibit platelet aggregation, thereby improving the blood flow velocity and patency rates 60 days after sdTEVG transplantation. A practical and reliable strategy for transforming "harmful" substances into "beneficial" factors at early transplantation stages is presented, which can also promote vascular transplantation in patients with hyperlipidemia., (© 2023 Wiley-VCH GmbH.)

The charge transport in quasi-2D perovskites limits their applications despite the superior stability and optoelectronic properties. Herein, a novel strategy is proposed to enhance the charge transport by regulating 3D perovskite phase in quasi-2D perovskite films. The carbohydrazide (CBH) as an additive is introduced into (PEA) 2 MA 3 Pb 4 I 13 precursors, which slows down the crystallization process and improves the phase ratio and crystal quality of the 3D phase. This structure change results in a significant improvement in charge transport and extraction, leading to the device demonstrating an almost 100% internal quantum efficiency, a peak responsivity of 0.41 A W -1 , and a detectivity of 1.31 × 10 12 Jones at 570 nm under 0 V bias. Furthermore, the air and moisture stability of (PEA) 2 MA 3 Pb 4 I 13 films is not deteriorated but gets significantly improved due to the better crystal quality and the passivation of defects by the residual CBH molecule. This work demonstrates a strategy for improving the charge transport properties of quasi-2D perovskites and also sheds light on solving the stability issue of 3D perovskite films via the proper passivation or additives, which will inspire the fast development of the perovskite community., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Low-grade heat is ubiquitous in the environment and its thermoelectric conversion by the ionic conductors remains a challenge because of the low efficiency and poor sustainability. Here we demonstrate that the thermoelectric performances can be boosted by combining the Soret effect of protons and proton-coupled electron transfer (PCET) reaction of benzoquinone and hydroquinone in hydrogels. An overall enhancement of thermopower (25.9 mV K -1 ), power factor (5 mW m -1  K -2 ), figure of merit (>2.4) and continuity of power output is achieved. Moreover, an energy-storage function can be achieved by the redox couple, and a retained power output of 27.7 %, or 14 mW m -2 for more than 3 hours is obtained by the re-balance of PCET reactants in the hydrogel after the removal of the temperature gradient., (© 2023 Wiley-VCH GmbH.)

A family of novel highly π-extended tetracyano-substituted acene diimides, named as tetracyanodiacenaphthoanthracene diimides (TCDADIs), have been synthesized using a facile four-fold Knoevenagel condensation strategy. Unlike conventional cyano substitution reactions, our approach enables access to a large π-conjugated backbone with the in-situ formation of four cyano substitutents at room temperature while avoiding extra cyano-functionalization reactions. TCDADIs decorated with different N-alkyl substituents present good solubility, near-coplanar backbones, good crystallinity, and low-lying lowest unoccupied molecular orbital energies of -4.33 eV, all of which contribute to desirable electron-transport performance when applied in organic field-effect transistors (OFET). The highest electron mobility of an OFET based on a 2-hexyldecyl-substituted TCDADI single crystal reaches 12.6 cm 2  V -1  s -1 , which is not only among the highest values for the reported n-type organic semiconductor materials (OSMs) but also exceeds that of most n-type OSMs decorated with imide units., (© 2023 Wiley-VCH Verlag GmbH.)

Two novel N-doped nonalternant nanoribbons (NNNR-1 and NNNR-2) featuring multiple fused N-heterocycles and bulky solubilizing groups were prepared via bottom-up solution synthesis. NNNR-2 achieves a total molecular length of 33.8 Å, which represents the longest soluble N-doped nonalternant nanoribbon reported to date. The pentagon subunits and doping of N atoms in NNNR-1 and NNNR-2 have successfully regulated their electronic properties, achieving high electron affinity and good chemical stability enabled by the nonalternant conjugation and electronic effects. When applied a laser pulse of 532 nm, the 13-rings nanoribbon NNNR-2 shows outstanding nonlinear optical (NLO) responses, with the nonlinear extinction coefficient of 374 cm GW -1 , much higher than those of NNNR-1 (96 cm GW -1 ) and the well-known NLO material C 60 (153 cm GW -1 ). Our findings indicate that the N-doping of nonalternant nanoribbons is an effective strategy to access another type of excellent material system for high-performance NLO applications, which can be extended to construct numerous heteroatom-doped nonalternant nanoribbons with fine-tunable electronic properties., (© 2023 Wiley-VCH GmbH.)

Confining dual atoms (DAs) within the van der Waals gap of 2D layered materials is expected to expedite the kinetic and energetic strength in catalytic process, yet is a huge challenge in atomic-scale precise assembling DAs within two adjacent layers in the 2D limit. Here, an ingenious approach is proposed to assemble DAs of Ni and Fe into the interlayer of MoS 2 . While inheriting the exceptional merits of diatomic species, this interlayer-confined structure arms itself with confinement effect, displaying the more favorable adsorption strength on the confined metal active center and higher catalytic activity towards acidic water splitting, as verified by intensive research efforts of theoretical calculations and experimental measurements. Moreover, the interlayer-confined structure also renders metal DAs a protective shelter to survive in harsh acidic environment. The findings embodied the confinement effects at the atom level, and interlayer-confined assembling of multiple species highlights a general pathway to advance interlayer-confined DAs catalysts within various 2D materials., (© 2023 Wiley-VCH GmbH.)

Lithium metal batteries are promising to become a new generation of energy storage batteries. However, the growth of Li dendrites and the volume expansion of the anode are serious constraints to their commercial implementation. Herein, a controllable strategy is proposed to construct an ultrathin 3D hierarchical host of honeycomb copper micromesh loaded with lithiophilic copper oxide nanowires (CMMC). The uniquely designed 3D hierarchical arrayed skeletons demonstrate a surface-preferred and spatial-selective effect to homogenize local current density and relieve the volume expansion, effectively suppressing the dendrite growth. Employing the constructed CMMC current collector in a half-cell, >400 cycles with 99% coulombic efficiency at 0.5 mA cm -2 is performed. The symmetric battery cycles stably for >2000 h, and the full battery delivers a capacity of 166.6 mAh g -1 . This facile and controllable approach provides an effective strategy for constructing high-performance lithium metal batteries., (© 2023 Wiley-VCH GmbH.)