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The erythro isomer of 1-Napthyl-1-(2-piperidyl)methanol, an efficient chiral modifier for asymmetric heterogeneous hydrogenation, was obtained as the major isomer (95%) in two steps while the threo isomer can be obtained as the major isomer (67%) in three steps. It is shown that the diastereomer determined as the erythro by NMR was indeed the erythro and that the first eluted (-)-enantiomer on CHIRALCEL OD-R or -RH columns has the (1R,2S) configuration.

The phenomenon of rapid migration of photogenerated charges in natural photosynthetic systems has motivated the design of efficient photocatalysts capable of fast charge separation and efficient reaction kinetics for photocatalytically assisted enrichment and separation of uranium U(VI) in uranium wastewater. In this study, we developed a biomimetic photocatalytic system MnO x /NH 2 -UiO-66-rGO (M/UiO-rGO) with spatially separated dual cocatalysts. Among them, rGO functions to capture electrons and participates in reduction reactions, while MnO x captures holes and participates in oxidation reactions. The M/UiO-rGO catalyst exhibits excellent performance in photocatalytic reduction of uranium (reaching 91.8% in 1 h), and even under natural light conditions, it exhibits excellent uranium removal ability (80.4%). Using multispectral coupling technology, we further confirmed that enriched uranium undergoes a continuous and complex reaction process of "capture-reduction-free radical oxidation-nucleation-crystallization". This work presents a viable strategy for designing biomimetic photocatalysts with efficient charge separation and rapid reaction kinetics for environmental purification purposes.

The coupling of lattice and heterostructure interfaces represents an effective strategy for disrupting the so-called scalar relationship and accelerating reactions involving multiple intermediates. In view of this, a lattice-heterostructure interfacial catalyst consisting of a crystalline Fe/Ni bimetallic MOF and amorphous Fe-MOF was designed in this paper for high-performance alkaline oxygen evolution reaction electrocatalysis. The strongly coupled lattice-heterostructure interface induces a unique synergistic effect that promotes electron transfer of the catalyst. The resulting catalyst exhibits exceptionally high catalytic activity for the oxygen evolution reaction in alkaline media, the Ni 9 Fe 1 -BDC-1@Fe-MOF coated on a glassy carbon electrode has an overpotential of 257 mV at a current density of 10 mA cm -2 . Furthermore, this catalyst demonstrates a high electrochemical stability. These research results highlight the superiority of lattice-heterostructure interfaces in the development of advanced catalysts.

Gold nanorods (GNRs) as plasmonic metal nanoparticles are valuable for optical applications due to their tunable plasmonic properties. However, conventional colloidal GNRs face significant optical instability during storage, which limits their practical use. In this work, we developed a highly dispersible GNR powder using an octadecyl trimethylammonium bromide (C 18 TAB)-assisted freeze-drying method, preserving the optical and chemical sensing properties of GNRs for over 4 months. Compared with C 16 TAB, C 18 TAB significantly enhances the GNRs dispersibility even at lower concentrations. Our study demonstrates that C 18 TAB forms a sponge-like crystal structure that prevents aggregation during the freeze-drying process. The resulting GNR powder retains its plasmonic features and water dispersibility, achieving near-identical optical properties to those of fresh GNR solutions. This stability enabled creation of a liquid-free colorimetric test kit with a long shelf life. This work marks a significant step forward in the use of GNRs as standard analytical reagents, opening new avenues for real-world applications.

Restricted by the physical properties of materials, most traditional metasurfaces (MSs) cannot achieve transparent stealth in the visible spectrum. Although some metasurfaces for holography have been designed, there is no standard method for evaluating the advancement of wavefront manipulation under different design algorithms. Here, a complex-amplitude metasurface with optical transparency (OT) and full-space manipulation is presented in the millimeterwave band. Through frequency multiplexing, two holographic images "HOLO" and "GRAM" with high quality are designed, achieving the signal-to-noise ratios of 14.6 and 14.4 dB, respectively. The 64 × 64 bilayered metasurface consists of glass and poly(ethylene terephthalate) (PET) substrates and three metallic mesh layers. By change of the opening size and oriented angle of split rings, phase and amplitude modulations are independently realized. Besides, a new method is provided to assess the superiority of the metasurface holography system for near-field energy regulation. The prototype was fabricated using micro-nano-technology and tested. Two holographic images were experimentally demonstrated and show good agreement with theoretical calculations and simulated results. With the advantages of OT and full-space complex-amplitude customization, the proposed metasurface holograms for frequency-multiplexed may find prospective application aspects in target perception, multichannel data storage and encryption, and many other related fields.

The advancement of acid-stable oxygen evolution reaction (OER) electrocatalysts is crucial for efficient hydrogen production through proton exchange membrane (PEM) water electrolysis. Unfortunately, the activity of electrocatalysts is constrained by a linear scaling relationship in the adsorbed evolution mechanism, while the lattice-oxygen-mediated mechanism undermines stability. Here, we propose a heterogeneous dual-site oxide pathway mechanism (OPM) that avoids these limitations through direct dioxygen radical coupling. A combination of Lewis acid (Cr) and Ru to form solid solution oxides (Cr x Ru 1- x O 2 ) promotes OH adsorption and shortens the dual-site distance, which facilitates the formation of *O radical and promotes the coupling of dioxygen radical, thereby altering the OER mechanism to a Cr-Ru dual-site OPM. The Cr 0.6 Ru 0.4 O 2 catalyst demonstrates a lower overpotential than that of RuO 2 and maintains stable operation for over 350 h in a PEM water electrolyzer at 300 mA cm -2 . This mechanism regulation strategy paves the way for an optimal catalytic pathway, essential for large-scale green hydrogen production.

Metal-oxide interfaces play a critical role in catalytic processes, such as methanol adsorption and decomposition reactions. In this work, we investigated methanol reactions on the inverse model CeO 2 /Ag(111) catalyst surfaces, i.e., submonolayer CeO 2 films on Ag(111), under ultrahigh vacuum (UHV) conditions to specially address the role of CeO 2 -Ag interface in the catalytic methanol decomposition reactions. Using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and synchrotron radiation photoemission spectroscopy (SRPES), we found that, at the submonolayer ceria coverages, the CeO 2 nanoislands exhibit a hexagonal CeO 2 (111) lattice with fully oxidized Ce 4+ on Ag(111). At higher ceria coverages, multilayer ceria nanoislands form on the Ag(111) surface instead of a well-ordered film. A combination of temperature-programmed desorption (TPD) and SRPES reveals that methanol adsorbs dissociatively on the CeO 2 /Ag(111) surfaces at 110 K, resulting in the formation of methoxy groups. These methoxy groups subsequently decompose via two pathways: (i) interaction with lattice oxygen to produce formate species at 230 K, which then decompose to CO, and (ii) direct dehydrogenation of methoxy to formaldehyde. Notably, the surface with submonolayer CeO 2 film on Ag(111) demonstrates low-temperature reactivity (440 K) for methoxy dehydrogenation to formaldehyde, which occurs at a much lower temperature, compared to the surface of multilayer CeO 2 on Ag(111) surface (530 K). This finding emphasizes that the CeO 2 -Ag(111) interfaces provide unique active sites for methoxy dehydrogenation reactions.

Typical antibody-drug conjugates (ADCs) with valine-alanine linkage, often conjugated with the amino group in payloads, face challenges when interacting with hydroxyl group-containing payloads. Herein, we introduced a transformative Val-Ala-based double self-immolative linker-payload platform, reshaping ADCs by optimizing hydroxyl group-containing payload integration. Utilizing this platform, FDA022-BB05 was successfully conjugated with the hydroxyl group-containing payload DXd using trastuzumab (FDA022) as the monoclonal antibody (mAb). FDA022-BB05 demonstrated enhanced stability, effective cathepsin B sensitivity, reduced cell proliferation, increased bystander killing, and targeted delivery. Notably, acute toxicity evaluations in diverse preclinical models indicated favorable safety profiles and tolerability, with a broad therapeutic index in HER2-positive and -negative xenografts. Overall, these compelling findings support the promising therapeutic potential of FDA022-BB05 , emphasizing the significance of diverse linker-payload platform strategies. This ADC is a valuable addition to targeted cancer therapy development, currently advancing through phase I clinical trials.

Microplastic (MP) contamination in soil has been of great concern, but the dynamic aging process and potential pathways of MPs in natural soil systems remain poorly understood. Herein, poly(vinyl chloride) microplastics (5% w/w) were weathered for 12 months in sandy soil, silty clay, and silt loam. The results showed that the continuous increase of C═O and O-H groups (rate constant, k = 0.080-0.424 m -1 ) with time was observed on the surface of MPs aging in sandy soil due to the leading role of • OH induced by light irradiation. In the loam soil, the abundant coating of aluminosilicates and iron oxides on the MP surface by the formation of mineral-hydroxyl groups inhibited the generation of the C═O group ( k < 0.165 m -1 ). The k of the characteristic bond C-Cl during the first 9 months was 9.51 and 1.93 times higher in clay compared to that in sandy and loam soil, respectively, revealing that dechlorination triggered the first step of the aging process for MPs in clay owing to the participation of degrading bacteria ( Phenylobacterium and Caulobacteraceae ). The results provide important insights into the aging dynamics of MPs in environmentally realistic circumstance, which account for understanding the different aging processes of MPs in different soils.

Acute kidney injury (AKI) is a dynamic process associated with inflammation, oxidative stress, and lipid peroxidation, in which mitochondrial mitophagy and macrophage polarization play a critical role in the pathophysiology. Based on the expression of the CD44 receptor on renal tubular epithelial cells (RTECs) and activated M1 macrophages being abnormally increased, accompanied by up-regulation of reactive oxygen species (ROS) during AKI, the conjugates of bilirubin (BR), an endogenous antioxidant which has the property of anti-inflammation, and chondroitin sulfate (CS) with CD44-targeting property could be a promising therapeutic carrier. In this study, we develop a CD44-targeted/ROS-responsive CS-BR-mediated multifunctional liposome loading celastrol (CS-BR@CLT) for the targeted therapy of AKI. CS-BR@CLT is shown to selectively accumulate in AKI mouse kidneys via targeting of CD44 receptors. Treatment with CS-BR@CLT significantly ameliorates acute kidney injury caused by ischemia-reperfusion and protects renal function. Mechanistically, CS-BR@CLT inhibits apoptosis, protects mitochondria, promotes autophagy, regulates macrophage polarization, and alleviates interstitial inflammation. Overall, our study demonstrates that CS-BR@CLT could be a promising strategy to ameliorate acute kidney injury.

Ancient humans used dietary plants and herbs to treat disease and to pursue eternal life. Today, phytochemicals in dietary plants and herbs have been shown to be the active ingredients, some of which have antiaging and longevity-promoting effects. Here, we summarize 210 antiaging phytochemicals in dietary plants and herbs, systematically classify them into 8 groups. We found that all groups of phytochemicals can be categorized into six areas that regulate organism longevity: ROS levels, nutrient sensing network, mitochondria, autophagy, gut microbiota, and lipid metabolism. We review the role of these processes in aging and the molecular mechanism of the health benefits through phytochemical-mediated regulation. Among these, how phytochemicals promote longevity through the gut microbiota and lipid metabolism is rarely highlighted in the field. Our understanding of the mechanisms of phytochemicals based on the above six aspects may provide a theoretical basis for the further development of antiaging drugs and new insights into the promotion of human longevity.

A multinuclear Er-containing Dawson-type poly(selenotungstate) (poly(ST)) [H 2 N(CH 3 ) 2 ] 12 Na 8 Cs 6 H 26 [Er 12 Se 14 W 12 O 72 (H 2 O) 6 (Se 2 W 14 O 52 ) 6 ]·78H 2 O ( 1 ) was made by the one-pot assembly with an excess SeO 3 2- source in the reaction system. The polyoxoanion consists of an extremely rare Er 12 Se 14 W 12 O 72 (H 2 O) 6 ({Er 12 Se 14 W 12 }) cluster core surrounded by six tetravacant Dawson-type Se 2 W 14 O 52 ({Se 2 W 14 }) fragments, representing the most Se-containing Dawson-type structure so far. Notably, the {Er 12 Se 14 W 12 } cluster exhibits an interesting trefoil-shaped configuration, formed by the condensation of a central Er 3 Se 2 O 6 ({Er 3 Se 2 }) cage with three Er 3 Se 4 W 4 O 22 (H 2 O) 2 ({Er 3 Se 4 W 4 }) clusters. The catalytic performance of 1 was evaluated by the oxidative decontamination of 2-chloroethyl ethyl sulfide (CEES) into nontoxic 2-chloroethyl ethyl sulfoxide (CEESO), showing remarkable conversion and selectivity, as well as excellent reusability.

Anomalous thermal behaviors of excitonic luminescence in CsPbBr 3 perovskite quantum dots (PQDs) were observed. It is found that the main luminescence peak originated from the excitonic radiative recombination assisted by the longitudinal-optical (LO) phonon, and its integrated intensity first declines as the temperature varies from 10 to 150 K and then turns to increase at ∼160 K, reaching a maximum value at 300 K. A model considering the thermal detrapping and transfer of electrons from a trap level is developed to interpret these abnormal thermal behaviors of the luminescence from the PQDs. On the other hand, the quantum-mechanical multimode Brownian oscillator model was employed to unravel that the Huang-Rhys factor exclusively characterizing the exciton-phonon coupling in the studied CsPbBr 3 PQDs decreases from 1.65 at 10 K to 1.31 at 200 K.

The monitoring of radioactive iodide levels is of great significance in environmental science and cancer radiotherapy. In this work, a high-throughput, radiation-resistant, and visualized electrochemiluminescence (ECL) strategy was developed for detection of iodide ions. Herein, the hydrophobic ruthenium derivative (Ru(bpy) 3 [B(C 6 F 5 ) 4 ] 2 ) (bpy = bipyridyl) was doped in tertiary amine-coupled polymer dots (N-PFO Pdots) to synthesize self-enhanced Pdots (Ru@Pdots), which showed extremely high ECL intensity in absence of coreactant. Due to the efficient ECL resonance energy transfer between Ru(bpy) 3 [B(C 6 F 5 ) 4 ] 2 and N-PFO, the Ru@Pdots exhibited 18 times higher ECL intensity compared with bare N-PFO Pdots. Besides, Ru@Pdots also showed 220-times higher ECL intensity compared with Ru(bpy) 3 [B(C 6 F 5 ) 4 ] 2 doped coreactant-dependent Pdots (Ru@PFO Pdots). Using Ru@Pdots as ECL emitters, an ECL imaging array was designed for iodide ion detection, which exhibited a detection range of 0.8 nM-4 μM and a limit of detection of 0.1 nM. In this strategy, iodide ions were oxidized as iodide free radicals on the surface of the electrode, which could further consume the nitrogen radical of Ru@Pdots and effectively quench the ECL signal. This method also showed good specificity, radiation-resistant performance, and accuracy in actual seawater sample testing, which indicated its value in marine environmental monitoring, nuclear security, and cancer radiotherapy.

Enamel adhesion is acknowledged as durable; however, achieving long-lasting dentin adhesion remains a formidable challenge due to degradation of exposed collagen matrix after acid-etching of dentin. The idea of developing an enamel-like adhesion interface holds great promise in achieving enduring dentin adhesion. In this study, we constructed an enamel-like adhesion interface using a rapid remineralization strategy comprising an acidic primer and a rapid remineralization medium. Specifically, the acidic primer of 10-methacryloyloxydecyl dihydrogen phosphate (MDP) and epigallocatechin-3-gallate (EGCG) nanocomplex (MDP@EGCG primer) was utilized to partially demineralize dentin within 30 s, and the MDP@EGCG nanocomplex showed a strong interaction with exposed collagen, enhancing collagen remineralization properties. Then, the rapid remineralization medium containing polyaspartate (Pasp) stabilized amorphous calcium and phosphorus nanoclusters (rapid Pasp-CaP) was applied to modified dentin collagen for 1 min, which caused rapid collagen remineralization within a clinically acceptable time frame. This strategy successfully generated an inorganic rough and porous adhesive interface resembling etched enamel, fundamentally addressed issues of collagen exposure, and achieved durable dentin adhesion in vitro and in vivo while also ensuring user-friendliness. It exhibited potential in prolonging the lifespan of adhesive restorations in clinical settings. In addition, it holds significant promise in the fields of caries and dentin sensitivity treatment and collagen-based tissue engineering scaffolds.

A precise recording of electrophysiological signals requires high-performance flexible bioelectrodes to build a robust skin interface. The past decade has witnessed encouraging progress in the development of elastomeric electrodes for wearable electrophysiological monitoring; however, it remains challenging to achieve excellent flexibility, conformal contact, and high durability simultaneously. Herein, we report on an effective method to fabricate flexible yet durable microneedle electrodes (MEs) based on vertically aligned gold nanowires (Au NWs) embedded polyimide (PI), which meet the above three design requirements. The Au NWs embedded PI MEs could build conformal contact with human skin and maintain electrical stability with minimal contact impedance by effectively penetrating the stratum corneum of the skin. In comparison studies, we found our MEs outperformed conventional gel or elastomeric soft electrodes. We further integrated the vertical Au-NW MEs into a wearable healthcare system and achieved wireless real-time recordings of electromyography (EMG) and electrocardiography (ECG) with high signal-to-noise ratios (SNRs) and low motion artifacts. Our fabrication strategy opens a new route to improve the durability and reliability of emerging nanomaterial-based soft bioelectrodes for long-term wearable healthcare applications.

The aging process of microplastics (MPs) affects their surface physicochemical properties, thereby influencing their behaviors in releasing harmful chemicals, adsorption of organic contaminants, sinking, and more. Understanding the aging process is crucial for evaluating MPs' environmental behaviors and risks, but tracing the aging process remains challenging. Here, we propose a multimodal deep learning model to trace typical aging factors of aged MPs based on MPs' physicochemical characteristics. A total of 1353 surface morphology images and 1353 Fourier transform infrared spectroscopy spectra were achieved from 130 aged MPs undergoing different aging processes, demonstrating that physicochemical properties of aged MPs vary from aging processes. The multimodal deep learning model achieved an accuracy of 93% in predicting the major aging factors of aged MPs. The multimodal deep learning model improves the model's accuracy by approximately 5-20% and reduces prediction bias compared to the single-modal model. In practice, the established model was performed to predict the major aging factors of naturally aged MPs collected from typical environment matrices. The prediction results aligned with the aging conditions of specific environments, as reported in previous studies. Our findings provide new insights into tracing and understanding the plastic aging process, contributing more accurately to the environmental risk assessment of aged MPs.

Rapid real-time PCR (generally <1 h) has broad prospects. In this study, we synthesized a new type of nanomaterial core-shell tecto-dendrimer coated with Au nanoparticles (Au CSTDs) for research in this field. The experimental results showed that Au CSTDs could significantly shorten the time of real-time PCR (from 72 to 28 min) with different templates, while the detection limit reached 10 copies and the nonspecific amplification was significantly reduced. Furthermore, experimental analyses and theoretical studies using the finite element simulation method confirmed that Au CSTDs function by synergistically enhancing electrostatic adsorption and thermal conductivity. These properties play a key role in improving real-time PCR, especially in particle-particle interactions. This study contributes an advanced method to rapid real-time PCR, which is expected to remarkably improve the efficiency, lower the detection limit, and enhance the specificity of molecular detection.

Developing surfaces that effectively repel low-surface-tension liquids with tunable adhesive properties remains a pivotal challenge. Micronano hierarchical re-entrant structures emerge as a promising solution, offering a robust structural defense against liquid penetration, minimizing area fraction, and creating narrow gaps that generate substantial upward Laplace pressure. However, the absence of an efficient, scalable, and tunable construction method has impeded their widespread applications. Here, drawing inspiration from springtail epidermal structures, octopus suckers, and rose petals, we present a scalable manufacturing strategy for artificial micronano hierarchical T-shaped structures. This strategy employs double-transfer UV-curing nanoimprint lithography to form nanostructures on microstructured surfaces, offering high structural tunability. This approach enables precise control over topography, feature size, and arrangement of nano- and microscale sections, resulting in superamphiphobic surfaces that exhibit high contact angles (>150°) and tunable adhesive forces for low-surface-energy liquids. These surfaces can be applied to droplet-based microreactors, programmable droplet-transfer systems, and self-cleaning surfaces suitable for various liquids, particularly those with low surface tension. Remarkably, we have also succeeded in fabricating the hierarchical structures on flexible and transparent substrates. We demonstrate the advantages of this strategy in the fabrication of hierarchical micronanostructures, opening up a wide range of potential applications.

Advanced biosensors must exhibit high sensitivity, reliability, and convenience, making them suitable for detecting trace samples in biological or medical applications. Currently, biometric identification is the predominant method in clinical practice, but it is complex and time-consuming. In this study, we propose an optical metasurface utilizing the Fano resonance effect, which exhibits a sharp resonance with a transmittance of 32% at 0.65 THz. The resonance dip has a narrow bandwidth of 0.07 THz and a high Q -factor of 42. This resonance arises from the coupling of bright and dark modes, underpinned by the electromagnetic mechanism of Fano resonance. We integrated the metasurface into a microfluidic platform and fabricated low-temperature gallium arsenide photoconductive antennas (LT-GaAs-PCAs) on both sides of the microfluidics to efficiently generate and detect THz waves, significantly reducing the system's volume. The biosensor's detection limits for Escherichia coli ( E. coli ) and cefamandole nafate are 5 × 10 3 cells/mL and 5 μg/mL, respectively. Experimentally, when E. coli and cefamandole nafate solutions were sequentially injected into the microfluidic chip, a blue shift in the spectrum was observed. The sensor measured a 95.2% killing rate of E. coli by 40 μg/mL cefamandole nafate solution, with only a 3% deviation from biological experiments. Additionally, a timed killing experiment using 40 μg/mL cefamandole nafate on E. coli revealed a 93.7% killing rate within 3 min. This research presents a THz microfluidic biosensor with rapid detection, high sensitivity, and enhanced portability and integration, offering a promising approach for biomedical research, including antibiotic efficacy assessment and bacterial concentration monitoring.

The development of functional nanomaterials is crucial for advancing personalized and precision medicine. Graphene-metal nanocrystal hybrid materials not only possess the intrinsic advantages of graphene-based materials but also exhibit additional optical, magnetic, and catalytic properties of various metal nanocrystals, showing great synergies in bioapplications, including biosensing, bioimaging, and disease treatments. In this Perspective, we discuss the advantages and design principles of graphene-metal nanocrystal hybrid materials and provide an overview of their applications in biological fields. Finally, we highlight the challenges and future directions for their practical implementation.

Breaking the trade-off between activity and stability of supported metal catalysts has been a long-standing challenge in catalysis, especially for metal nanoparticles (NPs) with high hydrogenation activity but poor stability. Herein, we report a porous poly(divinylbenzene) polymer-supported Pd NP catalyst (Pd/PDVB) with both high activity and excellent stability for the solvent-free hydrogenation of nitrobenzene, even at ambient temperature (25 °C) and H 2 pressure (0.1 MPa). Pd/PDVB gave a turnover frequency as high as 22,632 h -1 at 70 °C and 0.4 MPa, exceeding 5556 h -1 of the classical Pd/C catalyst under equivalent conditions. Mechanistic studies reveal that the polymer support benefits the desorption of the aniline product from the Pd surface, which is crucial for rapid hydrogenation under solvent-free conditions. In addition, the polymer support in Pd/PDVB efficiently hindered Pd leaching, resulting in good stability.

Electrochemical hydrogenation of aldehyde molecules, exemplified by 5-hydroxymethylfurfural (HMF), offers a sustainable approach for synthesizing higher value-added alcohols. However, severe coupling side reactions impede its practical implementation at high concentrations. In this work, a cluster-level heterostructure of a PMo 12 /Cu catalyst is synthesized by loading Keggin-type phosphomolybdic acid (H 3 PMo 12 O 40 , PMo 12 ) onto Cu nanowires. The catalyst exhibits high selectivity in electrocatalytic hydrogenation (ECH) of HMF to 2,5-bishydroxymethylfuran (BHMF) under an unprecedentedly high substrate concentration of 1.0 M. Under -0.3 V (vs RHE) with 1.0 M HMF, PMo 12 /Cu shows a Faradaic efficiency as high as 98% with an excellent productivity of 4.35 mmol cm -2 h -1 toward BHMF, much higher than those on the pristine Cu nanowires. Mechanism studies and density functional theory calculations demonstrate that the heterostructural interface of PMo 12 /Cu serves as an active reaction center for the ECH. The unique electronic properties and geometric structure promote the dissociative reduction of water molecules to generate H* and reduce HMF with a decreased reaction energy barrier, which is responsible for exceptional reactivity and selectivity.

Utilizing softly confined self-assembly at the water surface represents a promising approach for the fabrication of two-dimensional molecular monolayers (2D MMs), which have predominantly been concentrated on amphiphilic organic compounds before. Herein, we introduce a straightforward method termed "water surface-assisted molecular deposition (WSAMD)" to organize nonamphiphilic molecules into dense monolayers with high reproducibility. To underscore the versatility and merit of this methodology in the field of supramolecular electronics, we have successfully fabricated a range of defect-free, uniform semiconducting polymer monolayers, featuring a thickness reflective of molecular architectures. The charge carrier mobility could reach 0.05 cm 2 V -1 s -1 for holes and 3.5 × 10 -4 cm 2 V -1 s -1 for electrons, respectively, in p-type and n-type polymeric monolayers when tested as the active layer in field-effect transistors. Furthermore, in situ polymerization reactions can be exploited to generate conductive monolayers of macromolecules such as polybenzylaniline (PBnANI) and polypyrrole (PPy), where PBnANI monolayers exhibit channel length-dependent conductivity, up to 0.37 S cm -1 . The advent of the WSAMD method heralds a significant leap forward in the advancement of molecular 2D materials, catalyzing new avenues of exploration within material chemistry.

The structural, photophysical, and photochemical properties of Ln(depma)(hmpa) 2 (NO 3 ) 3 (Ln = La, Ce, Nd, Sm, Eu, Tb, Ho, Er, and Yb) complexes 1-Ln were investigated with a multidisciplinary approach involving synthesis, photocycloaddition-based crystal engineering, spectroscopic analytical techniques and quantum chemical ab initio calculations. Depending on the Ln 3+ ion the isostructural 1-Ln complexes exhibit quite different behavior upon excitation at 350-400 nm. Some 1-Ln complexes (Ln = La, Ce, Sm, Tb, Yb) emit a broad and strong band near 533 nm arising from paired anthracene moieties, whereas others (Ln = Nd, Eu, Ho, Er) do not. 1-Eu is not emissive at all, whereas 1-Nd , 1-Ho , and 1-Er exhibit a Ln 3+ based luminescence. Upon irradiation with 365 nm ultraviolet (UV) light 1-Ln (Ln = La, Ce, Sm, Tb, Yb) dimerize by means of a photochemically induced [4 + 4] cycloaddition of the anthracene moieties, whereas 1-Ln (Ln = Nd, Eu, Ho, Er) remain monomers. We propose three models, based on the matching of the energy levels between the Ln 3+ ion and the paired or dimerized anthracene units in the energy-resonance crossing region, as well as on internal conversion-driven and intersystem crossing-driven energy transfer, which explain the Ln 3+ ion regulated photophysics and photochemistry of the 1-Ln complexes., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Firefighting foam is a significant source of per- and polyfluoroalkyl substances (PFAS) pollution, yet the PFAS profiles in foam formulations, particularly in China, remain unclear. Here, using target and nontarget analyses, we investigated 50 target PFAS in firefighting foams currently utilized in China, identified novel PFAS, and discovered new end products through a total oxidizable precursor (TOP) assay. We identified a total of 54 PFAS compounds (spanning 34 classes and containing seven novel PFAS) with total PFAS concentrations of 0.03-21.21 mM. Among seven novel PFAS, four PFAS met persistence, bioaccumulation, and toxicity criteria, and another PFAS had the highest ToxPi score among the identified 54 PFAS. Moreover, the predominant PFAS varied significantly in the studied foams and differed markedly from those used in other countries. After the TOP assay, nontarget analysis uncovered 1.1-55.5% more PFAS precursors and 8.25-55.5% more fluorine equivalents compared to traditional target analysis combined with TOP assay. Specifically, three double-bond perfluorinated alcohols were identified for the first time as end products of the TOP assay. This study provides crucial information for pollution control and risk assessment associated with PFAS in firefighting foam applications and emphasizes the importance of combining nontarget analysis with TOP assay in uncovering unknown PFAS precursors.

Visualizing the whole vascular network system is crucial for understanding the pathogenesis of specific diseases and devising targeted therapeutic interventions. Although the combination of light sheet microscopy and tissue-clearing methods has emerged as a promising approach for investigating the blood vascular network, leveraging the spatial resolution down to the capillary level and the ability to image centimeter-scale samples remains difficult. Especially, as the resolution improves, the issue of photobleaching outside the field of view poses a challenge to image the whole vascular network of adult mice at capillary resolution. Here, we devise a fluorescent microsphere vascular perfusion method to enable labeling of the whole vascular network in adult mice, which overcomes the photobleaching limit during the imaging of large samples. Moreover, by combining the utilization of a large-scale light-sheet microscope and tissue clearing protocols for whole-mouse samples, we achieve the capillary-level imaging resolution (3.2 × 3.2 × 6.5 μm) of the whole vascular network with dimensions of 45 × 15 × 82 mm in adult mice. This method thus holds great potential to deliver mesoscopic resolution images of various tissue organs for whole-animal imaging.

Ribosome profiling and mass spectrometry have revealed thousands of previously unannotated small and alternative open reading frames (sm/alt-ORFs) that are translated into micro/alt-proteins in mammalian cells. However, their prevalence across human tissues and biological roles remains largely undefined. The placenta is an ideal model for identifying unannotated microproteins and alt-proteins due to its considerable protein diversity that is required to sustain fetal development during pregnancy. Here, we profiled unannotated microproteins and alt-proteins in human placental tissues from preeclampsia patients or healthy individuals by proteomics, identified 52 unannotated microproteins or alt-proteins, and demonstrated that five microproteins can be translated from overexpression constructs in a heterologous cell line, although several are unstable. We further demonstrated that one microprotein, XRCC6P1, associates with translation initiation factor eIF3 and negatively regulates translation when exogenously overexpressed. Thus, we revealed a hidden sm/alt-ORF-encoded proteome in the human placenta, which may advance the mechanism studies for placenta development as well as placental disorders such as preeclampsia.

n-Type polythiophene represents a promising category of n-type polymer thermoelectric materials known for their straightforward structure and scalable synthesis. However, n-type polythiophene often suffers from a twisted backbone and poor stacking property when introducing high-density electron-withdrawing groups for a lower lowest unoccupied molecular orbital (LUMO) level, which is considered to be beneficial for n-doping efficiency. Herein, we developed two isomers of polythiophene derivatives, PTTz1 and PTTz2, by inserting thiazole units into the polythiophene backbone composed of thieno[3,4- c ]pyrrole-4,6-dione (TPD) and thiophene-3,4-dicarbonitrile (2CNT). Although PTTz1 and PTTz2 share a similar polymer skeleton, they differ in thiazole configuration, with the nitrogen atoms of the thiazole units oriented toward TPD and 2CNT, respectively. The insertion of thiazole units significantly planarizes the polythiophene backbone while largely preserving low LUMO levels. Notably, PTTz2 exhibits a more coplanar backbone and closer π-stacking compared to PTTz1, resulting in a greatly enhanced electron mobility. Both PTTz1 and PTTz2 can be easily n-doped due to their deep LUMO levels. PTTz2 demonstrates superior thermoelectric performance, with an electrical conductivity of 50.3 S cm -1 and a power factor of 23.8 μW m -1 K -2 , which is approximately double that of PTTz1. This study highlights the impact of the thiazole unit on n-type polythiophene derivatives and provides valuable guidelines for the design of high-performance n-type polymer thermoelectric materials.

Nanoplastics (NPs) are widely detected in the atmosphere and are likely to be deposited on plant leaves. However, our understanding of their foliar uptake, translocation, and trophic transfer profiles is limited due to a lack of quantitative analytical tools to effectively probe mechanisms of action. Here, using synthesized deuterium ( 2 H) stable isotope-labeled polystyrene nanoplastics ( 2 H-PSNPs), the foliar accumulation and translocation of NPs in lettuce and the dynamics of NP transfer along a lettuce-snail terrestrial food chain were investigated. Raman imaging and scanning electron microscopy demonstrated that foliar-applied NPs aggregated on the leaf surface, entered the mesophyll tissue via the stomatal pathway, and eventually translocated to root tissues. Quantitative analysis showed that increasing levels of foliar exposure to 2 H-PSNPs (0.1, 1, and 5 mg/L in spray solutions, equivalent to receiving 0.15, 1.5, and 7.5 μg/d of NPs per plant) enhanced NP accumulation in leaves, with concentrations ranging from 0.73 to 15.6 μg/g (dw), but only limited translocation (<5%) to roots. After feeding on 5 mg/L 2 H-PSNP-contaminated lettuce leaves for 14 days, snails accumulated NPs at 0.33 to 10.7 μg/kg (dw), with an overall kinetic trophic transfer factor of 0.45, demonstrating trophic dilution in this food chain. The reduced ingestion rate of 3.18 mg/g/day in exposed snails compared to 6.43 mg/g/day can be attributed to the accumulation of 2 H-PSNPs and elevated levels of chemical defense metabolites in the lettuce leaves, which decreased the palatability for snails and disrupted their digestive function. This study provides critical quantitative information on the characteristics of airborne NP bioaccumulation and the associated risks to terrestrial food chains.

Piezoelectric catalysis could convert mechanical energy into chemical energy, which can combine with solar energy for a high-efficiency piezo-photocatalysis reaction. In this work, NiTiO 3 nanorods were synthesized via the sol-gel method and initially employed for the removal of U(VI) from radioactive-contaminated water. The NiTiO 3 nanorods will generate an internal electric field in an ultrasonic environment, which could greatly improve the performance of piezo-photocatalysis in reducing U(VI) by promoting the generation of photoexcited electrons and reactive oxygen species (ROS). After exposure to visible light and ultrasound for 3 h, the NTO-R-1 exhibited superb U(VI) degradation efficiency of 93.91%, which was 2.58, 6.15, and 6.68 times greater than those of visible light, ultrasonic irradiation, and dark, respectively. Moreover, photoexcited electrons and oxygen-active species play a decisive role in the piezo-photocatalysis process. Therefore, NiTiO 3 with excellent piezo-photocatalysis properties exhibits good potential for the development of efficient wastewater purification catalysts and also helps to probe the possible mechanism of piezo-photocatalysis removal of U(VI) in wastewater.

Multiphase Pickering emulsions, including two or more active agents, are of great importance to effectively manage complicated wounds. However, current strategies based on Pickering emulsions are still unsatisfying since they involve only stabilization by inactive particles and encapsulation of the hydrophobic drugs in the oil phase. Herein, thyme essential oil (TEO) was encapsulated in the shell of functional tea polyphenol (TP)-curcumin (Cur) nanoparticles (TC NPs) to exemplarily develop a novel Pickering emulsion (TEO/TC PE). Hydrophobic Cur was loaded with hydrophilic TP to obtain TC NPs, and under homogenization, these TC NPs adsorbed on the surface of TEO droplets to form a stable core-shell structure. Owing to such an oil-in-water (O/W) structure, the sequential release of the first Cur from pH-responsive disintegrated TC NPs and then the leaked TEO from the emulsion yielded synergetic functions of TEO/TC PE, leading to enhanced antibacterial, biofilm elimination, antioxidant, and anti-inflammatory activities. This injectable TEO/TC PE was applied to treat the infected full-thickness skin defects, and satisfactory wound healing effects were achieved with rapid angiogenesis, collagen deposition, and skin regeneration. The present TEO/TC PE constituted entirely of plant-sourced active products is biosafe and expected to spearhead the future development of novel wound dressings.

Although vanadium-based compounds possess several advantageous characteristics, such as multivalency, open structure, and high theoretical specific capacity, which render them highly promising candidates for cathode materials in aqueous zinc ion batteries (AZIBs), their large-scale application still necessitates addressing the challenges posed by slow kinetics resulting from low conductivity and capacity degradation caused by material dissolution. Therefore, we have successfully synthesized high-purity mixed multivalent (NH 4 ) 8 [V IV 12 V V 7 O 41 (OH) 9 ]·11H 2 O (NVO) crystalline materials via a liquid-phase precipitation modulation method and employed it as an innovative AZIB cathode material for the first time. It exhibits a remarkable reversible specific capacity of 240 and 102.2 mAh g -1 after undergoing 1000 cycles at current densities of 1 and 5 A g -1 , respectively, highlighting its exceptional cycling stability and electrochemical performance. The results from cyclic voltammetry (CV) and GITT tests demonstrate that the dominant factor influencing the charge storage is the pseudocapacitive behavior, which is accompanied by an exceptionally high diffusion coefficient of Zn 2+ at a rate of 10 -10 cm 2 s -1 . The highly reversible intercalation-deintercalation of Zn 2+ in NVO/Zn cells is demonstrated through ex-situ TEM, XRD, and XPS analyses. This work provides a benchmark for the development of high-performance POV electrode materials.

Cesium lead iodide light-emitting diodes (LEDs) are attractive for displays due to their Rec. 2020 red standard compliance. However, achieving high current efficiencies (CEs), which is important for displays, is challenging because their emission spectrum is near the tail of the photopic luminosity function. Substituting some iodine with bromine can improve CEs by enlarging the bandgap, but defects easily form in iodine-bromine mixed perovskites. Here, we successfully reduced defect formation by adding organic ammonium salts and zwitterions. The organic ammonium salts do not form low-dimensional perovskites under the hydrogen bonding interaction of zwitterions. Instead, they passivate the cesium vacancy by forming new hydrogen bonds after perovskite crystallization. This approach leads to a red perovskite LED with a high CE of 12.8 cd A -1 and a peak external quantum efficiency of 20.3%, meeting the Rec. 2020 standard. It can be extended to large-area devices (2500 mm 2 ) without a significant efficiency loss.

Strain-free GaAs/AlGaAs semiconductor quantum dots (QDs) grown by droplet etching and nanohole infilling (DENI) are highly promising candidates for the on-demand generation of indistinguishable and entangled photon sources. The spectroscopic fingerprint and quantum optical properties of QDs are significantly influenced by their morphology. The effects of nanohole geometry and infilled material on the exciton binding energies and fine structure splitting are well-understood. However, a comprehensive understanding of GaAs/AlGaAs QD morphology remains elusive. To address this, we employ high-resolution scanning transmission electron microscopy (STEM) and reverse engineering through selective chemical etching and atomic force microscopy (AFM). Cross-sectional STEM of uncapped QDs reveals an inverted conical nanohole with Al-rich sidewalls and defect-free interfaces. Subsequent selective chemical etching and AFM measurements further reveal asymmetries in element distribution. This study enhances the understanding of DENI QD morphology and provides a fundamental three-dimensional structural model for simulating and optimizing their optoelectronic properties.

Carrier transport capacity with high mobility and long-range diffusion length holds particular significance for the advancement of modern optoelectronic devices. Herein, we have unveiled the carrier dynamics and transport properties of a pristine violet phosphorus (VP) nanosheet by a transient absorption microscopy. Under the excitation (2.41 eV) above the exciton band, two photoinduced absorption peaks with the energy difference of approximately 520 meV emerge within a broadband transient absorption background which originates from the prompt generation of free carriers and the concomitant formation of excitons (lifetime of 467.21 ps). This observation is consistent with the established band-edge model of VP. Intriguingly, we have determined the ambipolar diffusion coefficient and mobility of VP to be approximately 47.32 cm 2 ·s -1 and 1798 cm 2 ·V -1 ·s -1 , respectively, which further indicate a long-range carrier transport of approximately 2.10 μm. This work unveils the significant carrier transport capacity of VP, highlighting its potential for future optoelectronic and excitonic applications.

Antibody-drug conjugates (ADCs), which combine the precise targeting capabilities of antibodies with the powerful cytotoxicity of small-molecule drugs, have evolved into a promising approach for tumor treatment. However, the traditional covalent coupling method requires the design of a specific linker tailored to the properties of the small-molecule drugs, which greatly limits the development of ADCs and the range of drugs that can be used. Herein, a novel type of antibody-calixarene drug conjugates (ACDCs) that function similarly to ADCs by delivering drugs to their targets using antibodies but without the requirement of covalent conjugation of the drugs with antibodies is presented. By replacement of conventional linkers with supramolecular linkers, the ACDCs can load various chemotherapeutic drugs through host-guest interactions. Furthermore, ACDCs are readily reduced upon reaching the hypoxic microenvironment, resulting in rapid release of the drugs. With this precise drug encapsulation and controlled release mechanism, ACDCs deliver drugs to tumor tissues effectively and achieve a significantly enhanced antitumor effect. Considering that the ACDCs can be easily prepared by combining antibody-calixarene conjugates derived from tumor-targeting antibodies with various small-molecule drugs, ACDCs may provide a promising platform technology to accelerate ADC development and thus improve the therapeutic efficacy of chemotherapy.

Oral ulcers present as recurrent and spontaneous lesions, often causing intolerable burning pain that significantly disrupts patients' daily lives and compromises their quality of life. In addressing this clinical challenge, oral dissolving films (ODFs) have emerged as promising pharmaceutical formulations for oral ulcer management due to their rapid onset of action, ease of administration, and portability. In this study, ODFs containing the insoluble drug dexamethasone (Dex) were formulated for the treatment of oral ulcers in rabbits using a solvent casting method with ethanol as the solvent. To optimize the composition of the ODFs, a Box-Behnken Design (BBD) experiment was employed to investigate the effects of varying concentrations of hydroxypropyl cellulose (HPC), low-substituted hydroxypropyl cellulose (L-HPC), and plasticizer (glycerol) on key parameters, such as disintegration time, tensile strength, and peel-off efficiency of the films. Subsequently, the film properties of the Dex-loaded ODFs (ODF@Dex) were thoroughly assessed, revealing favorable attributes, including homogeneity, mechanical strength, and solubility. Notably, the use of ethanol as the solvent in the ODF preparation facilitated the homogeneous distribution of insoluble drugs within the film matrix, thereby enhancing their solubility and dissolution rate. Leveraging the potent pharmacological activity of Dex, ODF@Dex was further evaluated for its efficacy in promoting ulcer healing and mitigating the expression of inflammatory factors both in vitro and in vivo. The findings demonstrated that the ODF@Dex exerted significant antiulcer effects by modulating the PI3K/Akt signaling pathway, thus contributing to ulcer resolution. In conclusion, our study underscores the potential of HPC-based ODFs formulated with ethanol as a solvent as a promising platform for delivering insoluble drugs, offering a viable strategy for the clinical management of oral ulcers.

Migration of microplastics (MPs) in soil-groundwater systems plays a pivotal role in determining its concentration in aquifers and future threats to the terrestrial environment, including human health. However, existing models employing an advection-dispersion equation are insufficient to incorporate the holistic mechanism of MP migration. Therefore, to bridge the gap associated with MP migration in soil-groundwater systems, a dispersion-drag force coupled model incorporating a drag force on MPs along with dispersion is developed and validated through existing laboratory and field-scale experiments. The inclusion of the MP dispersion notably increased the global maximum particle velocity ( v maxp ) of MPs, resulting in a higher concentration of MPs in the aquifer, which is also established by sensitivity analysis of MP dispersion. Additionally, increasing irrigation flux and irrigation areas significantly accelerates MP migration downward from soil to deep saturated aquifers. Intriguingly, v maxp of MPs exhibited a nonlinear relationship with MPs' sizes smaller than 20 μm reaching the highest value (=1.64 × 10 -5 m/s) at a particle size of 8 μm, while a decreasing trend was identified for particle sizes ranging from 20 to 100 μm because of the hindered effect by porous media and the weaker effect of the drag force. Moreover, distinct behaviors were observed among different plastic types, with poly(vinyl chloride), characterized by the highest density, displaying the lowest v maxp and minimal flux entering groundwater. Furthermore, the presence of a heterogeneous structure with lower hydraulic conductivity facilitated MP dispersion and promoted their migration in saturated aquifers. The findings shed light on effective strategies to mitigate the impact of MPs in aquifers, contributing valuable insights to the broader scientific fraternity.

Passive radiative cooling technology without electric consumption is an emerging sustainability technology that plays a key role in advancing sustainable development. However, most radiative cooling materials are vulnerable to outdoor contamination and thermal/UV exposure, which leads to decreased performance. Herein, we report a hierarchically structured polyimide/zinc oxide (PINF/ZnO) composite membrane that integrates sunlight reflectance of 91.4% in the main thermal effect of the solar spectrum (0.78-1.1 μm), the mid-infrared emissivity of 90.0% (8-13 μm), UV shielding performance, thermal resistance, and ideal hydrophobicity. The comprehensive performance enables the composite membrane to yield a temperature drop of ∼9.3 °C, compared to the air temperature, under the peak solar irradiance of ∼800 W m -2 . In addition, the temperature drop of as-obtained composite membranes after heating at 200 °C for 6 h in a nitrogen/air atmosphere can be well maintained at ∼9.0 °C, demonstrating their ideal radiative cooling effect in a high-temperature environment. Additionally, the PINF/ZnO composite membrane shows excellent chemical durability after exposure to the outdoor environment. This work provides a new strategy to integrate chemical durability and thermal resistance with radiative cooling, presenting great potential for passive radiative cooling materials toward practical applications in harsh environments.

Microalgae, integral to marine ecosystems for their rich nutrient content, notably lipids and proteins, were investigated by using reversed-phase liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (RPLC-Q-TOF-MS/MS). This study focused on lipid composition in three commonly used microalgae species ( Spirulina platensis , Chlorella vulgaris , and Schizochytrium limacinum ) for functional food applications. The analysis unveiled more than 700 lipid molecular species, including glycolipids (GLs), phospholipids (PLs), sphingolipids (SLs), glycerolipids, and betaine lipids (BLs). GLs (19.9-64.8%) and glycerolipids (24.1-70.4%) comprised the primary lipid. Some novel lipid content, such as acylated monogalactosyldiacylglycerols (acMGDG) and acylated digalactosyldiacylglycerols (acDGDG), ranged from 0.62 to 9.68%. The analysis revealed substantial GLs, PLs, and glycerolipid variations across microalgae species. Notably, S. platensis and C. vulgaris displayed a predominance of fatty acid (FA) 18:2 and FA 18:3 in GLs, while S. limacinum exhibited a prevalence of FA 16:0, collectively constituting over 60% of the FAs of GLs. In terms of PLs and glycerolipids, S. platensis and C. vulgaris displayed elevated levels of arachidonic acid (AA) and eicosapentaenoic acid (EPA), whereas S. limacinum exhibited a significant presence of docosahexaenoic acid (DHA). Principal component analysis (PCA) revealed MGDG (16:0/18:1), DG (16:0/22:5), Cer (d18:1/20:0), and LPC (16:1) as promising lipid markers for discriminating between these microalgae samples. This study contributes to a comprehensive understanding of lipid profiles in three microalgae species, emphasizing their distinct biochemical characteristics and potentially informing us of their high-value utilization in the food industry.

A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and styrenes including 1,1-, 1,2-disubstituted alkenes can be subjected to the protocol, and a wide range of vinyl sulfones was obtained in high to excellent yields with good functional group compatibility. Notably, the process did not allow the desulfonylation of sulfonyl chloride or chlorosulfonylation of alkenes. Radical-trapping experiment supported that a sulfonyl free-radical was likely produced and triggered subsequent transformation in the process.

Natural attenuation of organic contaminants can occur under anoxic or oxic conditions. However, the effect of the coupling anoxic-oxic process, which often happens in subsurface soil, on contaminant transformation remains poorly understood. Here, we investigated 2,4-dichlorophenol (2,4-DCP) transformation in Fe-rich soil under anoxic-oxic alternation. The anoxic and oxic periods in the alternating system showed faster 2,4-DCP transformation than the corresponding control single anoxic and oxic systems; therefore, a higher transformation rate (63.4%) was obtained in the alternating system relative to control systems (27.9-42.4%). Compared to stable pH in the alternating system, the control systems presented clear OH - accumulation, caused by more Fe(II) regeneration in the control anoxic system and longer oxygenation in the control oxic system. Since 2,4-DCP was transformed by ion exchangeable Fe(II) in soil via direct reduction in the anoxic process and induced · OH oxidation in the oxic process, OH - accumulation was unbeneficial because it competed for proton with direct reduction and inhibited • OH generation via complexing with Fe(II). However, the alternating system exhibited OH - -buffering capacity via anoxic-oxic coupling processes because the subsequent oxic periods intercepted Fe(II) regeneration in anoxic periods, while shorter exposure to O 2 in oxic periods avoided excessive OH - generation. These findings highlight the significant role of anoxic-oxic alternation in contaminant attenuation persistently.

The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m -2 h -1 (K + ), reaching excellent mono/multivalent selectivity up to 20.1 (K + /Mg 2+ ) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.

Cancer immunotherapy has yielded remarkable results across a variety of tumor types. Nevertheless, the complex and immunosuppressive microenvironment within solid tumors poses significant challenges to established therapies such as immune checkpoint blockade (ICB) and chimeric antigen receptor T-cell (CAR-T) therapy. Within the milieu, tumor-associated macrophages (TAMs) play a significant role by directly suppressing T-cell functionality and fostering an immunosuppressive environment. Effective regulation of TAMs is, therefore, crucial to enhancing the efficacy of immunotherapies. Various therapeutic strategies targeting TAM modulation have emerged, including blocking TAM recruitment, direct elimination, promoting repolarization toward the M1 phenotype, and enhancing phagocytic capacity against tumor cells. The recently introduced CAR macrophage (CAR-M) therapy opens new possibilities for macrophage-based immunotherapy. Compared with CAR-T, CAR-M may demonstrate superior targeting and infiltration capabilities toward solid tumors. This review predominantly delves into the origin and development process of TAMs, their role in promoting tumor growth, and provides a comprehensive overview of immunotherapies targeting TAMs. It underscores the significance of regulating TAMs in bolstering antitumor therapies while discussing the potential and challenges of developing TAMs as targets for immunotherapy.