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Nowadays, water splitting has been recognized as one of the most attractive ways to produce clean hydrogen energy. Herein, a novel sulfur-doped layered double-hydroxide (namely, S-NiCo-LDH) electrocatalyst with nanocage structure is prepared. After the etching treatment with Ni ions, the spatial structure of the catalysts is opened, and the hydrophilicity is improved, which will enhance the adsorption capacity for H 2 O to provide convenience for hydrogen evolution reaction (HER). Interestingly, the S doping can boost the capture capability toward OH - to create conditions for the occurrence of oxygen evolution reaction (OER). More importantly, the introduction of S element can improve the density of states located near the Fermi level of NiCo-LDH, thereby accelerating the electron transfer and increase the carrier density. Meanwhile, the existence of S element can remarkably reduce the energy barriers of *O and *H formation, boosting HER and OER in an alkaline solution. As a result, the S-NiCo-LDH electrocatalyst shows excellent performance in overall water splitting, affording low overpotentials of 168 and 235 mV at 10 mA/cm 2 for HER and OER, respectively. Furthermore, the S-NiCo-LDH electrocatalyst exhibits good long-term stability in both HER and the OER. In short, the current work can give a meaningful reference for future research.

Nanomaterials with peroxidase-like activity and photothermal conversion efficiency have garnered significant attention for their ability to generate cytotoxic hydroxyl radicals and provide synergistic therapeutic effects. Selecting nanozymes with suitable properties and carriers is crucial for maximizing efficacy. While the mucin family is known for its mucoadhesive, glycosylated structures that enhance drug bioavailability and targeting, its potential in nanozymes remains underexplored. Here, we utilize mucin-2 to facilitate osmium nanoclusters (Os@Mucin), creating protein-corona-like nanozymes. This configuration bestows Os@Mucin with excellent peroxidase-like activity (769 U/mg) and photothermal conversion efficiency (22.83%, 808 nm). Mucin-2 promotes Os uptake by cells, allowing Os@Mucin to exhibit tumor environment-responsive peroxidase-like activity, further enhanced under photothermal conditions for targeted cytotoxicity and synergistic effects. In vivo experiments demonstrate that this integration effectively treats triple-negative breast cancer. This study innovatively highlights the potential of the mucin family and underscores the promising role of Os nanozymes in tumor therapy.

Friction at sliding interfaces, even in the atomistically smooth limit, can proceed through many energy dissipation channels, such as phononic and electronic excitation. These processes are often entangled and difficult to distinguish, eliminate, and control, especially in the presence of wear. Structural superlubricity (SSL) is a wear-free state with ultralow friction that closes most of the dissipation channels, except for electronic friction, which raises a critical concern of how to effectively eliminate and control such a channel. In this work, we construct a Schottky junction between a microscale graphite flake and a doped silicon substrate in the SSL state to address the issue and achieve wide-range (by 6×), continuous, and reversible electronic friction tuning by changing the bias voltage. No wear or oxidation at the sliding interfaces was observed, and the ultralow friction coefficient indicated that electronic friction dominated the friction tuning. The mechanism of electronic friction is elucidated by perturbative finite element analysis, which shows that migration of the space-charge region leads to drift and diffusion of charge carriers at Schottky junctions, resulting in energy dissipation.

In structures with special geometry lattices, variations in stacking sequences are ubiquitous, yielding many novel structures and functionalities. Despite a wealth of intriguing properties and wide-ranging applications, there remains a considerable gap in understanding the correlation between special geometry lattices and functionalities in borides. Here, we design and synthesize a new superconducting boride Nb 2 IrB 2 , with a body-centered orthorhombic structure, consisting of alternating two-dimensional [Nb-Ir-Nb] triple-triangular-lattice-layers and B fragment layers. Advanced aberration-corrected scanning transmission electron microscopy observations show variable stacking configurations between [Nb-Ir-Nb] triple-triangular-lattice layers that can be tuned through synthesis conditions. Density functional theory calculations reveal that the coherent low-energy boundary interface plane of {101} between [11̅1] and [010] domains is responsible for the variable stacking behaviors. Energetically favorable structures are thereby reasonably proposed, based on nanoscale imperfect structure units. These findings provide valuable insights for designing and exploring new structures and functionalities within boride systems involving special geometry lattices.

Group A rotaviruses (RVA) remain one of the dominant pathogens causing diarrhea in children under 5 years of age worldwide, despite a sharp decrease of RVA-associated diarrhea and mortality since the introduction of rotavirus vaccines. The decreased effectiveness of live attenuated rotavirus vaccines, coupled with the emergence of new rotavirus genotypes and the risk of cross-species virus transmission, underscores the necessity to develop more effective and broad-spectrum rotavirus vaccines. In this study, we utilized nanoparticles coupled with the SpyCatcher-SpyTag system to effectively display the truncated VP8-1 protein. The modular display of the monovalent VP8-1 proteins markedly increased the immunogenicity of VP8-1. Furthermore, the bivalent display of VP8-1 proteins from simian rotavirus SA11 and lamb rotavirus LLR on the same particle not only increased immunogenicity against homotypic antigens but also elicited robust heterotypic immune responses and conferred effective protection against a distant heterotypic rotavirus with sequence identities of only 62%-66% in an adult mouse model. Therefore, mosaic VP8 nanoparticles could be considered as a viable strategy for the development of the next-generation broad-spectrum rotavirus vaccine.

With the widespread utilization of moist wound dressings, the extended healing time and increased risk of wound infection caused by excessively moist environments have garnered significant attention. The development of hydrogel dressings that can effectively control the wound moisture level and promote healing is very important. Inspired by the pore-opening perspiration effect of the skin, this study constructed an injectable dual-network hydrogel, CMCS-OSA/AG/MXene, by the composition of a dynamic covalent network of carboxymethyl chitosan and oxidized sodium alginate based on the Schiff base and hydrogen bond network of the thermosensitive low-melting-point agar with the advantage of the upper critical solution temperature (UCST) effect. Under near-infrared (NIR) light stimulation, the CMCS-OSA/AG/MXene hydrogel shows characteristics conducive to rapid removal of wound exudate while maintaining an appropriate moist environment for the wound and excellent antibacterial effects with its photothermal responses. The excellent conductivity of the hydrogel can also promote cell proliferation under external electrical stimulation (ES). Further validation through animal experiments on a full-thickness skin defect model demonstrates the excellent capability of CMCS-OSA/AG/MXene in accelerating wound healing. This work provides an innovative approach to the development of injectable hydrogel dressing materials with inherent drainage functionality and shows a new avenue to wound moisture control and wound healing promotion.

Microwave-assisted photocatalysis offers a novel approach for degrading antibiotics, while the mechanism of enhancement of microwave-induced photocatalysis remains poorly understood. In this study, tetracycline (TC) was degraded using the method of microwave-assisted photocatalysis with a ZnO catalyst, which was synthesized by the combination of hydrothermal and calcination methods. The self-assembled mesoporous ZnO catalyst exhibited superior catalytic activity in degrading TC. It is found that the degradation efficiency of TC by the ZnO catalysts with microwave-assisted photocatalysis is 4.27 times higher than that of photocatalysis alone. Of particular significance, we found that the optical absorption range of ZnO increased and the band gap decreased when microwave was introduced into the photocatalytic system. Semi-in situ photochemical tests demonstrated that more photogenerated electron-hole pairs were detected under microwave, thus further improving the photocatalytic activity of ZnO. The separation efficiency and charge transfer efficiency of photogenerated electron-hole pairs also improved due to the increase of oxygen vacancies in the synergistic effect. Meanwhile, h + and ·OH were the main active species in the degradation system. The mechanism of microwave-induced photocatalysis is illustrated, and an efficient way for degrading antibiotic is provided in this work.

The limited active sites and faster photogenerated electron-hole pair recombination rate of g-C 3 N 4 restrict its application in photocatalytic H 2 production. Constructing heterojunctions has been shown to improve the spatial (directional) separation of photogenerated electrons and holes. However, due to interface mismatch in traditional heterojunction structures and a lack of precise electron transport channels, the photocatalytic efficiency is limited. Here, we developed a two-step calcination approach to create an Fe 2 N/g-C 3 N 4 heterojunction linked by Fe-O bonds (named as Fe-OCN). The newly formed Fe-O bonds within the heterojunction can act as atomic-level interface electron transfer channels, directly transferring the photogenerated electrons of g-C 3 N 4 to the reactive center Fe 2 N, significantly improving the charge transfer rate and utilization, thus promoting visible-light-driven photocatalytic H 2 production. The optimal Fe-OCN achieved a H 2 production rate of 5986.29 μmol g -1 h -1 under visible light, 13.44 times higher than that of the OCN due to efficient charge separation and transfer capabilities. This work provides a constructive reference for the design and synthesis of organic-inorganic heterojunction with chemically bonded interfaces, establishing quick electron transfer channels, and achieving targeted electron transfer.

The unripe fruit of the plant Momordica charantia L., commonly known as bitter gourd or bitter melon, is a popular vegetable and medical herb in many parts of the world and is characterized by its strong bitter taste. In our endeavor to decode its bitter taste, the dichloromethane fraction of 75% methanol extract of bitter gourd was found to be intensely bitter. Combining sensory analysis-guided fractionation and newly developed comparative high-pressure liquid chromatography (HPLC) analysis-guided purification led to the isolation of five known compounds including momordicoside L ( 1 ), (23 E )-3β- O -malonyl-7β,25-dihydroxycucurbita-5,23-dien-19-al ( 2 ), 3- O -β-d-allopyranosyl-7β,25-dihydroxycucurbita-5,23( E )-dien-19-al ( 3 ), momordicine IV ( 5 ), and charantoside B ( 6 ) and three new compounds 3- O -β-d-3-ketoglucopyranosly-7β,25-dihydroxycucurbita-5,23( E )-dien-19-al ( 4 ), 6'- O -malonylmomordicoside L ( 7 ), and 6'- O -malonylmomordicine IV ( 8 ) from bitter gourd. Sensory analysis revealed compounds 3 - 8 had strong bitter taste with their bitter taste recognition thresholds in the range between 3.6 ( 4 ) and 13.6 ppm ( 6 ) in 3% ethanol. UPLC-MS/MS quantification showed that their concentration in bitter gourd ranged from 16.5 ± 1.3 mg/kg ( 4 ) to 214.8 ± 14.0 mg/kg ( 6 ) on a dry weight basis. Calculation of the dose-over-threshold (DoT) factor showed that momordicine IV ( 5 ) and charantoside B ( 6 ) should be considered as bitter principles of bitter gourd. In addition, the study also demonstrated the ubiquity of the isomerization reaction in the side chain of cucurbitane-type triterpenoids. Many isolated compounds were the isomerized products of their natural precursors, and these precursors should be the primary bitterness contributors of fresh fruits. In addition, comparative HPLC analysis-guided purification could be a practical approach for the fast isolation of acid-labile precursors.

Serotonylation has been identified as a novel protein posttranslational modification for decades, where an isopeptide bond is formed between the glutamine residue and serotonin through transamination. Transglutaminase 2 (also known as TGM2 or TGase2) was proven to act as the main "writer" enzyme for this PTM, and a number of key regulatory proteins (including small GTPases, fibronectin, fibrinogen, serotonin transporter, and histone H3) have been characterized as the substrates of serotonylation. However, due to the lack of pan-specific antibodies for serotonylated glutamine, the precise enrichment and proteomic profiling of serotonylation still remain challenging. In our previous research, we developed an aryldiazonium probe to specifically label protein serotonylation in a bioorthogonal manner, which depended on a pH-controlled chemoselective rapid azo-coupling reaction. Here, we report the application of a photoactive aryldiazonium-biotin probe for the global profiling of serotonylation proteome in cancer cells. Thus, over 1,000 serotonylated proteins were identified from HCT 116 cells, many of which are highly related to carcinogenesis. Moreover, a number of modification sites of these serotonylated proteins were determined, attributed to the successful application of our chemical proteomic approach. Overall, these findings provided new insights into the significant association between cellular protein serotonylation and cancer development, further suggesting that to target TGM2-mediated monoaminylation may serve as a promising strategy for cancer therapeutics.

Contact engineering enhances electronic device performance and functions but often involves costly, inconvenient fabrication and material replacement processes. We develop an in situ , reversible, full-device-scale approach to reconfigurable 2D van der Waals contacts. Ideal p-type Schottky contacts free from surface dangling bonds and Fermi-level pinning are constructed at structurally superlubric graphite-MoS 2 interfaces. Pressure control is introduced, beyond a threshold of which tunneling across the contact can be activated and amplified at higher loads. Record-high figures of merits such an ideality factor nearing 1 and an off-state current of 10 -11 A were reported. The concept of on-device moving contacts is demonstrated through a wearless Schottky generator, operating with an optimized overall efficiency of 50% in converting weak, random external stimuli into electricity. The device combines generator and pressure-sensor functions, achieving a high current density of 31 A/m 2 and withstanding over 120,000 cycles, making it ideal for neuromorphic computing and mechanosensing applications.

Cobalt-based sulfides (CSs) are generally regarded as potentially valuable anode materials for sodium-ion batteries (SIBs) due to their excellent theoretical capacity and natural abundance. Nevertheless, their slow reaction kinetics and poor structural stability restrict the practical application of the materials. In this study, the dual-carbon-confined Se-CoS 2 @NC@C hollow nanocubes with anion doping are synthesized using ZIF-67 as the substrate by resorcin-formaldehyde (RF) encapsulation and subsequent carbonization and sulfurization/selenization. RF- and ZIF-67-derived dual-carbon skeleton hollow structures with a robust carbon skeleton and abundant internal space minimize cyclic stress, mitigate volume changes and maintain the structural integrity of the material. More importantly, Se doping increases the lattice spacing of CoS 2 , weakens the strength of Co-S bonds, and modulates the electronic structure around Co atoms, thereby optimizing the adsorption energy of the material. As a result, the hollow nanocubes of Se-CoS 2 @NC@C demonstrates excellent electrochemical performance as the anode for SIBs, delivering a high reversible capacity of 549.4 mAh g -1 at 0.5 A g -1 after 100 cycles and a superb rate performance (541.1 mAh g -1 at 0.2  A  g -1 , and 393.3 mAh g -1 at 5 A g -1 ). This study proposes a neoteric strategy for synthesizing advanced anodes for SIBs through the synergy of anion doping engineering and dual-carbon confinement strategy.

Methyl iodide (CH 3 I) gas as a toxic gas causes great harm to organisms due to its high volatility and high reactivity with biological nucleophiles. Unfortunately, the sensing and detection of CH 3 I gas are challenging because of the diffusive nature of the gases and its low concentrations in the environment. Herein, we have developed a fast, green, and sensitive CH 3 I gas visual sensing method based on the capture technology of toxic gases by natural deep eutectic solvents (NADESs) coupled to the halide rapid exchange capability of perovskite nanocrystals (PNCs). In this strategy, NADESs are used as an absorption solution to adsorb gaseous CH 3 I, while simultaneously exposing I - through the action of the nucleophilic reagent; then, CsPbBr 3 PNCs were synthesized in NADESs and used as sensing material to achieve I - exchange. Benefiting from the capture and enrichment of CH 3 I gas, the sensitivity of the gas sensor was highly improved. The sensor exhibited the lowest detection limit (limits of detection) of 164.15 μmol/m 3 , below the minimum safe level for human inhalation, which is 200 μmol/m 3 . This breakthrough offers greater possibilities for the quantitative detection of CH 3 I gas.

The all-inorganic CsPbBr 3 perovskite solar cells exhibit excellent stability against humidity and thermal conditions as well as relatively low production cost, rendering them a gradually emerging research hot spot in the field of photovoltaics. However, the absence of a hole transport layer (HTL) in its common structure and the substantial energy level difference of up to 0.6 eV between the highest occupied molecular orbital (HOMO) level of CsPbBr 3 and the work function of the carbon electrode have emerged as the primary factor limiting the improvement of its power conversion efficiency (PCE). In this work, the monomer 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) is spin-coated onto the surface of the CsPbBr 3 film directly and then subjected to annealing; DBEDOT undergoes in situ polymerization to form poly(3,4-ethylenedioxythiophene) (PEDOT), which aims to ameliorate the issue of excessive energy level difference between CsPbBr 3 and the carbon electrode, and to facilitate the extraction and transport efficiency of holes between the CsPbBr 3 perovskite and the carbon electrode. Compared to the pristine device, the PCE of the device based on in situ polymerization is enhanced and achieves a maximum efficiency of 9.81%. Furthermore, the unencapsulated devices based on in situ polymerization maintain 95.9% of their original efficiency after 40 days of stability testing.

Accurately distinguishing tumor cells from normal cells is a key issue in tumor diagnosis, evaluation, and treatment. Fluorescence-based immunohistochemistry as the standard method faces the inherent challenges of the heterogeneity of tumor cells and the lack of big data analysis of probing images. Here, we have demonstrated a machine learning-driven imaging method for rapid pathological diagnosis of five types of cancers (breast, colon, liver, lung, and stomach) using a perovskite nanocrystal probe. After conducting the bioanalysis of survivin expression in five different cancers, high-efficiency perovskite nanocrystal probes modified with the survivin antibody can recognize the cancer tissue section at the single cell level. The tumor to normal (T/N) ratio is 10.3-fold higher than that of a conventional fluorescent probe, which can successfully differentiate between tumors and adjacent normal tissues within 10 min. The features of the fluorescence intensity and pathological texture morphology have been extracted and analyzed from 1000 fluorescence images by machine learning. The final integrated decision model makes the area under the receiver operating characteristic curve (area under the curve) value of machine learning classification of breast, colon, liver, lung, and stomach above 90% while predicting the tumor organ of 92% of positive patients. This method demonstrates a high T/N ratio probe in the precise diagnosis of multiple cancers, which will be good for improving the accuracy of surgical resection and reducing cancer mortality.

The currently available immune checkpoint therapy shows a disappointing therapeutic efficacy for glioblastoma multiforme (GBM), and it is of great importance to discover better immune checkpoints and develop innovative targeting strategies. The discovered metabolic immune checkpoint ecto-5-nucleotidase (CD73) in a tumor contributes to its immune evasion due to the dysregulation of extracellular adenosine (ADO), which significantly inhibits the function of antitumor T cells and increases the activity of immunosuppressive cells. Herein, we drastically inhibit the expression of CD73 to reduce the production of ADO by using versatile Au@Cu 2- x Se nanoparticles (ACS NPs). ACS NPs can decrease the expression of CD73 by alleviating the tumor hypoxia through their Fenton-like reaction to weaken the ADO-driven immunosuppression for enhancing antitumor T cell infiltration and activity of GBM. The copper ions (Cu 2+ ) released from ACS NPs can chelate with disulfide, leading to the formation of cytotoxic bis( N , N -diethyldithiocarbamate)-copper complex (CuET), which can be combined with radiotherapy to recruit more antitumor T cells to infiltrate into the tumor site. Based on the inhibition of CD73 to promote the infiltration and activity of antitumor T cells, a cascade of enhancing GBM immunotherapy effects can be achieved. The significant increase in CD8 + T and CD4 + T cells within the tumor and the memory T cells in the spleen effectively reduces tumor size by 92%, which demonstrates the excellent efficacy of immunotherapy achieved by a combination of metabolic immune checkpoint CD73 inhibition with chemoradiotherapy. This work demonstrates that modulation of CD73-mediated tumor immunosuppression is an important strategy of improving the outcome of GBM immunotherapy.

When the particle size of energetic materials is reduced to the nanoscale, significant changes occur in their properties and behavior. In this work, compression processes of three RDX nanoparticles ( A , B , and C ) were simulated using ReaxFF-lg. The mechanical, structural, and energetic responses of RDX nanoparticles during compression were revealed and characterized. Simulations reveal that the compression process of the nanoparticles can be divided into three stages: elastic stage, primary damage stage, and sustained damage stage. The temperature increase rate in the elastic phase is much lower than in the primary damage phase. In addition, we found that the smaller nanoparticle B presents a smaller elastic modulus and compressive strength, and it has a slower rate of temperature increase during the primary damage phase. Compared to cuboidal nanoparticles ( A and B ), the spherical nanoparticle C tends to absorb less energy during the elastic stage and exhibits slower damage rate during the primary damage stage. This is a key factor contributing to the low sensitivity of spherical nanoparticles.

Starter cultures play a significant role in lipid hydrolysis, prevention of lipid oxidation, and synthesis of fatty acid in fermented sausage, enhancing product quality. In this study, five synergistic bacterial strains were used, including Pediococcus pentosaceus (B-3), Latilactobacillus sakei DLS-24 (D-24), Latilactobacillus acidophilus DLS-29 (D-29), Lactiplantibacillus pentosus (B-1), and Lactiplantibacillus plantarum (B-2). Sausage B1B3D24 gave the highest free fatty acid with 39.45 g/100 g at 45-Day. Based on 2-thiobarbituric acid reactive substance, B2B3 contains 112.68 MDA/kg. Lipoxygenase activity displays the lowest in B1B3D24 with 0.095 μmol/min·mg followed by B2B3 with 0.145 μmol/min·mg. B1B3D24 contains 11.35 g/kg of monounsaturated fatty acid with the highest content in eicosenoic acid (C20:1) and palmitoleic acid (C16:1). The fatty acid synthesis pathway in B1B3D24 contains an active positive interaction with PUFA to increase the isotopomers of ω-3 and ω-6 fatty acids. In addition, lipid mediating genes in B1B3D24 show the highest counts in fatty-acid synthase, carbonyl reductase 4, 3-oxoacyl-[acyl-carrier-protein] synthase III, hydroxysteroid 17-beta dehydrogenase 8, and acetyl-CoA carboxylase.

Solid-state refrigeration based on the barocaloric effect is an effective alternative to traditional vapor compression refrigeration. Here 1-dodecanol has been studied due to its large latent heat at a solid-liquid phase transition point around room temperature. The transition temperature will vary with the applied hydrostatic pressure, exhibiting with a sensitivity of 0.14 K MPa -1 , which indicates its potential for refrigeration. A pressure of 40 MPa can result in a large isothermal entropy change of 520 J kg -1 K -1 (equivalent to that obtained in vapor compression refrigeration) at 297 K. A large adiabatic temperature change of >20 K in 1-dodecanol was acquired by direct measurement. A wide temperature window of ∼50 K (288-337 K) can be obtained in 1-dodecanol, which demonstrates broad application prospects. These discoveries offer promising prospects for barocaloric cooling and high-efficiency refrigeration technologies relying on solid-liquid phase transitions.

To effectively solve the problem of significant loss of transplanted cells caused by thrombosis during cell transplantation, this study simulates the human fibrinolytic system and combines metabolic oligosaccharide engineering with strain-promoted azide-alkyne cycloaddition (SPAAC) click chemistry to construct a cell surface with fibrinolytic activity. First, a copolymer (POL) of oligoethylene glycol methacrylate (OEGMA) and 6-amino-2-(2-methylamido)hexanoic acid (Lys) was synthesized by reversible addition-fragmentation chain transfer (RAFT) copolymerization, and the dibenzocyclooctyne (DBCO) functional group was introduced into the side chain of the copolymer through an active ester reaction, resulting in a functionalized copolymer DBCO-PEG4-POL with ε-lysine ligands. Then, azide functional groups were introduced onto the surface of HeLa model cells through metabolic oligosaccharide engineering, and DBCO-PEG4-POL was further specifically modified onto the surface of HeLa cells via the SPAAC "click" reaction. In vitro investigations revealed that compared with unmodified HeLa cells, modified cells not only resist the adsorption of nonspecific proteins such as fibrinogen and human serum albumin but also selectively bind to plasminogen in plasma while maintaining good cell viability and proliferative activity. More importantly, upon the activation of adsorbed plasminogen into plasmin, the modified cells exhibited remarkable fibrinolytic activity and were capable of promptly dissolving the primary thrombus formed on their surfaces. This research not only provides a novel approach for constructing transplantable cells with fibrinolytic activity but also offers a new perspective for effectively addressing the significant loss of transplanted cells caused by thrombosis.

Receptor tyrosine kinase-like orphan receptor 1 (ROR1) is an oncogenic membrane protein in several malignancies and has been considered an attractive target for the treatment of human cancers. In this study, structure-based virtual screening and structure optimization were conducted to identify novel ROR1 inhibitors. Based on hit compound 2 , 45 novel ROR1 inhibitors were designed and synthesized, and the detailed structure-activity relationship was investigated. Representative compound 19h potently binds ROR1 with a K D value of 0.10 μM, exhibiting antitumor activity in lung cancer and breast cancer cell lines (IC 50 : 0.36-1.37 μM). Additionally, a mechanism investigation demonstrated that compound 19h induces the apoptosis of tumor cells. Importantly, compound 19h significantly suppressed tumor growth in a mouse model without obvious toxicity. Overall, this work identified compound 19h as a new ROR1 inhibitor, providing a novel lead compound for the treatment of lung cancer and breast cancer.

Histone dopaminylation is a newly identified epigenetic mark that plays a role in the regulation of gene transcription, where an isopeptide bond is formed between the fifth amino acid of H3 (i.e., glutamine) and dopamine. Recently, we developed a chemical probe to specifically label and enrich histone dopaminylation via bioorthogonal chemistry. Given this powerful tool, we found that histone H3 glutamine 5 dopaminylation (H3Q5dop) was highly enriched in colorectal tumors, which could be attributed to the high expression level of its regulator, transglutaminase 2 (TGM2), in colon cancer cells. Due to the enzyme promiscuity of TGM2, nonhistone proteins have also been identified as dopaminylation targets; however, the dopaminylated proteome in cancer cells still remains elusive. Here, we utilized our chemical probe to enrich dopaminylated proteins from colorectal cancer cells in a bioorthogonal manner and performed the chemical proteomics analysis. Therefore, 425 dopaminylated proteins were identified, many of which are involved in nucleic acid metabolism and transcription pathways. More importantly, a number of dopaminylation sites were identified and attributed to the successful application of our chemical probe. Overall, these findings shed light on the significant association between cellular protein dopaminylation and cancer development, further suggesting that targeting these pathways may become a promising anticancer strategy.

Histone monoaminylation ( i.e ., serotonylation and dopaminylation) is an emerging category of epigenetic mark occurring on the fifth glutamine (Q5) residue of H3 N-terminal tail, which plays significant roles in gene transcription. Current analysis of histone monoaminylation is mainly based on site-specific antibodies and mass spectrometry, which either lacks high resolution or is time-consuming. In this study, we report the development of chemical probes for bioorthogonal labeling and enrichment of histone serotonylation and dopaminylation. These probes were successfully applied for the monoaminylation analysis of in vitro biochemical assays, cells, and tissue samples. The enrichment of monoaminylated histones by the probes further confirmed the crosstalk between H3Q5 monoaminylation and H3K4 methylation. Finally, combining the ex vivo and in vitro analyses based on the developed probes, we have shown that both histone serotonylation and dopaminylation are highly enriched in tumor tissues that overexpress transglutaminase 2 (TGM2) and regulate the three-dimensional architecture of cellular chromatin.

Two-dimensional semiconductor materials with vertical dipoles are promising photocatalysts as vertical dipoles not only promote the electron-hole separation but also enhance the carrier redox ability. However, the influence of vertical dipoles on carrier recombination in such materials, especially the competing relationship between vertical dipoles and band gaps, is not yet clear. Herein, first-principles calculations and nonadiabatic molecular dynamics simulations were combined to clarify the influence of band gap and vertical dipole on the carrier lifetime in Janus MoSSe monolayer. By comparing with the results of MoS 2 and MoSe 2 as well as exploring the carrier lifetime of MoSSe under strain regulation, it has been demonstrated that the vertical dipole, rather than the band gap, is the dominant factor affecting the carrier lifetime. Strikingly, a linear relationship between the carrier lifetime and vertical dipole is revealed. These findings have important implications for the design of high-performance photocatalysts and optoelectronic devices.

Superhydrophobicity-enabled jumping-droplet condensation and frosting have great potential in various engineering applications, ranging from heat transfer processes to antifog/frost techniques. However, monitoring such droplets is challenging due to the high frequency of droplet behaviors, cross-scale distribution of droplet sizes, and diversity of surface morphologies. Leveraging deep learning, we develop a semisupervised framework that monitors the optical observable process of condensation and frosting. This system is adept at identifying transient droplet distributions and dynamic activities, such as droplet coalescence, jumping, and frosting, on a variety of superhydrophobic surfaces. Utilizing this transient and dynamic information, various physical properties, such as heat flux, jumping characteristics, and frosting rate, can be further quantified, conveying the heat transfer and antifrost performances of each surface perceptually and comprehensively. Furthermore, this framework relies on only a small amount of annotated data and can efficiently adapt to new condensation conditions with varying surface morphologies and illumination techniques. This adaptability is beneficial for optimizing surface designs to enhance condensation heat transfer and antifrosting performance.

The delivery of proteins into the cytosol holds great promise for cell signaling manipulation and the development of precision medicine. However, this potency is challenged by achieving targeted and controlled delivery, specifically within diseased cells. In this study, we introduce a versatile and effective method for the precision delivery of therapeutic proteins to cancer cells by designing polyphenol-assisted biomineralization of zeolite imidazole framework-8 (ZIF-8). We demonstrate that by leveraging the strong noncovalent binding affinity of epigallocatechin gallate (EGCG) with both proteins and ZIF-8, our approach significantly enhances the biomineralization of ZIF-8, which in turn improves the efficiency of protein encapsulation and intracellular delivery. Moreover, the incorporation of EGCG within ZIF-8 enables controlled degradation of the nanoparticles and the selective release of the encapsulated proteins in cancer cells. This selective release is triggered by the oxidation of EGCG in response to the high levels of reactive oxygen species (ROS) found within cancer cells that destabilize the EGCG/ZIF-8 nanoparticles. We have further demonstrated the ability of EGCG/ZIF-8 to deliver a wide range of proteins into cancer cells, including bacterial virulence protein, to rewire cell signaling and prohibit tumor cell growth in a mouse xenograft model. Our strategy and findings underscore the potential of designing the EGCG/ZIF-8 interface for specific and controlled protein delivery for targeted cancer therapy.

Organic single crystals (OSCs) with uniform morphologies and highly ordered molecular aggregations are promising for high-performance optoelectronic devices, such as organic solid-state lasers (OSSLs), organic light-emitting transistors (OLETs), and organic light-emitting diodes (OLEDs). However, manipulating OSC morphologies and aggregation is challenging. In this study, we synthesized two-dimensional (2D) OSCs of 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) in hexagonal and parallelogram microplate (H-MP and P-MP) forms. Both types exhibit H-aggregation in the 2D plate plane but with different molecular transition dipole moment (TDM) orientations. This leads to different photon coupling modes with H-MP and P-MP microcavities. H-MPs enable isotropic 2D-waveguiding, forming whispering gallery mode (WGM) resonators, while P-MPs create unidirectional waveguiding, forming Fabry-Pérot mode (FP) resonators. These resonators can generate low-threshold laser emissions at 467 and 473 nm, respectively, and exhibit superior lasing stability with a half-life exceeding 2 h. Our BSBCz microplate OSCs are attractive candidates to combine controlled organic microcavities with photon transporting for realizing future integrated optoelectronic devices.

Revealing low-dimensional material growth dynamics is critical for crystal growth engineering. However, in a practical high-temperature growth system, the crystal growth process is a black box because of the lack of heat-resistant imaging tools. Here, we develop a heat-resistant optical microscope and embed it in a chemical vapor deposition (CVD) system to investigate two-dimensional (2D) crystal growth dynamics. This in situ optical imaging CVD system can tolerate temperatures of ≤900 °C with a spatial resolution of ∼1 μm. The growth of monolayer MoS 2 crystals was studied as a model for 2D crystal growth. The nucleation and growth process have been imaged. Model analysis and simulation have revealed the growth rate, diffusion coefficient, and spatial distribution of the precursor. More importantly, a new vertex-kink-ledge model has been suggested for monolayer crystal growth. This work provides a new technique for in situ microscopic imaging at high temperatures and fundamental insight into 2D crystal growth.

Na 3 V 2 (PO 4 ) 2 F 3 is recognized as a promising cathode for high energy density sodium-ion batteries due to its high average potential of ∼3.95 V (vs Na/Na + ). A high-voltage-resistant electrolyte is of high importance due to the long duration of 4.2 V (vs Na/Na + ) when improving cyclability. Herein, a targeted electrolyte containing additives with two -C≡N groups like succinonitrile has been designed. In this design, one -C≡N group is accessible to the solvation sheath and enables the other -C≡N in dinitrile being exposed and subsequently squeezed into the electric double layer. Then, the squeezed -C≡N group is prone to a preferential adsorption on the electrode surface prior to the exposed -CH 2 /-CH 3 in Na + -solvent and oxidized to construct a stable and electrically insulating interface enriched CN - /NCO - /Na 3 N. The Na 3 V 2 (PO 4 ) 2 F 3 -based sodium-ion batteries within a high-voltage of 2-4.3 V (vs Na/Na + ) can accordingly achieve an excellent cycling stability (e.g., 95.07% reversible capacity at 1 C for 1,5-dicyanopentane and 98.4% at 2 C and 93.0% reversible capacity at 5 C for succinonitrile after 1000 cycles). This work proposes a new way to design high-voltage electrolytes for high energy density sodium-ion batteries.

Capillary flow has garnered significant attention due to its unique dynamic characteristics that require no external force. Creating a quantitative analytical model to evaluate capillary flow behaviors in root-like networks is essential for enhancing fluid control properties in functional textiles. In this study, we explore the capillary dynamics within root-like networks under the influence of gravity and derive the most rapid capillary flow via structural optimization. The flow time in a capillary is dominated by the capillary pressure, viscous pressure loss, and gravity, each of which exhibits diverse sensitivities to the structures of root-like networks. We scrutinize various structural parameters to understand their impact on capillary flow in root-like networks. Subsequently, optimal structural parameters (namely, the mother tube diameter and diameter ratio) are identified to minimize capillary flow time. Moreover, we discovered that the correlation between flow time and distance for capillary flow in root-like networks does not obey the classical Lucas-Washburn equation. These results affirm that root-like networks can enhance capillary flow, providing critical insights for numerous capillary-flow-dependent engineering applications.

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N 3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N 3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

Prussian blue analogues receive tremendous attention owing to their spacious three-dimensional skeleton, high theoretical specific capacity, facile synthesis procedure, and high cost-effectiveness as among the most promising candidates for cathode materials in sodium-ion batteries (SIBs). Nonetheless, the practical specific capacity, especially under high current, is particularly frail due to the sluggish ion diffusion. In this study, the strategy of Ni substitution and formation of water-coordinated Fe is applied to lower the crystal field energy and elevate the active low-spin (LS) Fe content, which leads to a capacitive sodium storage mechanism, resulting in a substantial specific capacity under high current density. The delivered specific capacity of PW-325@2NiFe-55 is 95 mAh g -1 at 50 C, which is 72.5% capacity retention of the one at 0.5 C. Also, it maintains 80.2% of its initial specific capacity after 500 cycles at 5 C. Furthermore, a hypothesis of a joint diffusion-controlled and capacitive mechanism for high-spin (HS) Fe and a mere capacitive mechanism for LS Fe is put forward and verified through potentiastatic tests, operando 57 Fe Mössbauer spectroscopy, and ex situ XRD, which provides a new horizon to enhance the electrochemical performance for SIBs.

The relaxation of hot electrons in semiconductors is pivotal for both energy harvesting processes and optoelectronics. Utilizing a self-developed non-adiabatic molecular dynamics simulation approach in the momentum space (NAMD_ k ), we have examined the dynamics of hot electrons in silicon. Whether excited from the Γ or L point, the relaxation dynamics exhibit two distinct stages. Initially, within 100 fs, electrons scatter with phonons throughout the Brillouin zone. Subsequently, over a few picoseconds, they further relax toward the conduction band minimum as a whole. This picture of hot electron relaxation is highly consistent with the quasi-equilibrium hot electron ensemble (HEE) concept. Throughout the hot electron relaxation process, energy transfer to phonons is efficient, leading to time-dependent phonon excitation, which is thoroughly analyzed. This investigation provides a novel perspective on hot electron relaxation in silicon, which holds substantive implications for the realm of photovoltaic and optoelectronic device applications.

Achieving reliable detection of trace levels of NO 2 gas is essential for environmental monitoring and protection of human health protection. Herein, a thin-film gas sensor based on branched WO 3 /W 18 O 49 heterostructures was fabricated. The optimized WO 3 /W 18 O 49 sensor exhibited outstanding NO 2 sensing properties with an ultrahigh response value (1038) and low detection limit (10 ppb) at 50 °C. Such excellent sensing performance could be ascribed to the synergistic effect of accelerated charge transfer and increased active sites, which is confirmed by electrochemical impedance spectroscopy and temperature-programmed desorption characterization. The sensor exhibited an excellent detection ability to NO 2 under different air quality conditions. This work provides an effective strategy for constructing WO 3 /W 18 O 49 heterostructures for developing NO 2 gas sensors with an excellent sensing performance.

Protein drugs have been widely used in treating various clinical diseases because of their high specificity, fewer side effects, and favorable therapeutic effect, but they greatly suffer from their weak permeability through tissue barriers, high sensitivity to microenvironments, degradation by proteases, and rapid clearance by the immune system. Herein, we disrupted the standard protocol where protein drugs must be delivered as the cargo via a delivery system and innovatively developed a free entrapping matrix strategy by simply mixing bevacizumab (Beva) with zinc ions to generate Beva-NPs (Beva-Zn 2+ ), where Beva is coordinatively cross-linked by zinc ions with a loading efficiency as high as 99.2% ± 0.41%. This strategy was universal to generating various protein NPs, with different metal ions (Cu 2+ , Fe 3+ , Mg 2+ , Sr 2+ ). The synthetic conditions of Beva-NPs were optimized, and the generated mechanism was investigated in detail. The entrapment, releasing profile, and the bioactivities of released Beva were thoroughly studied. By using in situ doping of the fourth-generation polyamindoamine dendrimer (G 4 ), the Beva-G 4 -NPs exhibited extended ocular retention and penetration through biobarriers in the anterior segment through transcellular and paracellular pathways, effectively inhibiting corneal neovascularization (CNV) from 91.6 ± 2.03% to 13.5 ± 1.87% in a rat model of CNV. This study contributes to engineering of protein NPs by using a facile strategy for overcoming the weaknesses of protein drugs and protein NPs, such as weak tissue barrier permeability, low encapsulation efficiency, poor loading capacity, and susceptibility to inactivation.

The chlorine evolution reaction (CER) is essential for industrial Cl 2 production but strongly relies on the use of dimensionally stable anode (DSA) with high-amount precious Ru/Ir oxide on a Ti substrate. For the purpose of sustainable development, precious metal decrement and performance improvement are highly desirable for the development of CER anodes. Herein, we demonstrate that surface titanium oxide amorphization is crucial to regulate the coordination environment of stabilized Ir single atoms for efficient and durable chlorine evolution of Ti monolithic anodes. Experimental and theoretical results revealed the formation of four-coordinated Ir 1 O 4 and six-coordinated Ir 1 O 6 sites on amorphous and crystalline titanium oxides, respectively. Interestingly, the Ir 1 O 4 sites exhibited a superior CER performance, with a mass activity about 10 and 500 times those of the Ir 1 O 6 counterpart and DSA, respectively. Moreover, the Ir 1 O 4 anode displayed excellent durability for 200 h, far longer than that of its Ir 1 O 6 counterpart (2 h). Mechanism studies showed that the unsaturated Ir in Ir 1 O 4 was the active center for chlorine evolution, which was changed to the top-coordinated O in Ir 1 O 6 . This change of active sites greatly affected the adsorption energy of Cl species, thus accounting for their different CER activity. More importantly, the amorphous structure and restrained water dissociation of Ir 1 O 4 synergistically prevent oxygen permeation across the Ti substrate, contributing to its long-term CER stability. This study sheds light on the importance of single-atom coordination structures in the reactivity of catalysts and offers a facile strategy to prepare highly active single-atom CER anodes via surface titanium oxide amorphization.

Enhancing the performance of traditional pesticide formulations by improving their leaf surface wetting capabilities is a crucial approach for maximizing the pesticide efficiency. This study develops an emulsifiable concentrate (EC) of 4.5% β-cypermethrin containing Brucea javanica oil (BJO). The incorporation of BJO aims to improve the leaf-wetting properties of the EC formulation and enhance its insecticidal effectiveness. The droplet size and emulsion characteristics of β-CYP EC emulsion with varying concentrations of the emulsifier were evaluated, and changes after incorporating BJO were assessed to develop the optimal formulation. A comprehensive comparison was conducted among commercial 4.5% β-cypermethrin EC (β-CYP EC-1), 4.5% β-cypermethrin EC with BJO (β-CYP EC-2), and 4.5% β-cypermethrin EC without BJO (β-CYP EC-3). This comparison encompassed various factors including storage stability, insecticidal activity, cytotoxicity, and wetting performance on cabbage leaves. The results indicated that the ideal emulsifier concentration was 15% emulsifier 0201B. β-CYP EC-2 demonstrated superior wetting properties on cabbage leaves (the wetting performance of β-CYP EC-2 emulsion on cabbage leaves is 2.60 times that of the β-CYP EC-1 emulsion), heightened insecticidal activity against the third larvae of Plutella xylostella [diamondback moth (DBM)] [the insecticidal activity of the β-CYP EC-2 emulsion against the third larvae of DBM is 1.93 times that of the β-CYP EC-1 emulsion (12 h)], and more obvious inhibitory effects on the proliferation of DBM embryo cells than the other tested formulations. These findings have significant implications for advancing pest control strategies and promoting sustainable and effective agricultural practices.

Dendritic cell (DC)-based vaccines have shown promise in adoptive cell therapy for enhancing the antigen-specific response of antitumor immunity. However, their clinical efficacy is limited by the less-presented tumor-associated antigens (TAAs) through MHC I and low lymph node homing efficiency. Herein, to address these issues, we rationally design and fabricate DC-based nanovaccines by coating Cu 2- x Se nanoparticles (CS NPs) with the membrane of matured DCs (named as DCNV(CSD) nanovaccines). We reveal the important roles of CS NPs in the DCNV(CSD) nanovaccines from three aspects: (1) inducing the immunogenic cell death of tumor cells to expose abundant TAAs; (2) promoting the escape of TAAs from the lysosomes of DCs during the antigen presenting process through MHC I; (3) sustainably releasing traces of copper ions to promote the proliferation of T cells. Our DCNV(CSD) nanovaccines are characterized with high expressions of MHC I, CD80, CD86, CCR7, and ICAM-1 proteins, which not only endow them with abundantly processed specific TAAs, but also a strong capability of homing to the lymph nodes. The homing capability of our small DCNV(CSD) nanovaccines is better than that of matured DCs. More importantly, they can elicit the strong response of potent antispecific CD8 + T cells for antitumor immunotherapy, as tested in the treatment of highly invasive glioblastoma and highly metastatic melanoma. Additionally, DCNV(CSD) nanovaccines can generate memory T cells (T EM ) in the spleen of mice to effectively prevent the recurrence of treated tumors. This work demonstrates a universal approach to fabricate high-performance DC-based nanovaccines for tumor immunotherapy by using versatile CS NPs.

Refrigeration technology based on the caloric effect is one of the more environmentally friendly alternatives to gas compression refrigeration. The barocaloric effect utilizes pressure to induce phase transition and results in a large entropy change. In this work, a colossal barocaloric effect in the liquid-solid transition (L-S-T) of binary fatty acid methyl esters (BFAMEs) was discovered. At 295 K, an isothermal entropy change as high as 591 J kg -1 K -1 and a reversible entropy change of 356 J kg -1 K -1 at a hydrostatic pressure of 80 MPa were obtained by mixing methyl palmitate and methyl stearate with a specific ratio to synthesize a BFAME. The value of the isothermal entropy change of the BFAME is comparable to that of a commercial gas compression refrigerant, R134a. This work will provide a new L-S-T candidate material to replace commercial refrigerants for the potential application of caloric effect refrigeration technology.

Presently, piezoelectric materials are gradually playing a significant role within composites to improve the damping and vibrational attenuation capacities of host composites. Previous studies paid attention to isolating the mechanical damping contribution and piezoelectric contribution of polymer-based piezoelectric composites (PPCs). However, reports detailing the piezoelectric damping of such materials have not paid sufficient attention to the technologies and methods to improve the piezoelectric damping of PPCs. In this study, we propose novel damping polyurethane (PU)-based piezoelectric composites with carbon-coated piezoelectric fillers (PZT@C/PU) with improved piezoelectric damping ability. The mechanical damping and piezoelectric damping of composites were theoretically decoupled, and we elaborate on the mechanism enhancing piezoelectric damping through the carbon coating strategy by comparing with the composites with nonpiezoelectric fillers. The as-fabricated core-shell structure having an optimized interface exhibits the proposed PZT@C/PU composite pads with relatively prominent damping ability (loss factor tan δ max = 1.0, tan δ RT = 0.3), ductility (400.63%), and sound isolating behavior (transmission loss TL > 23 dB). Moreover, the vibration test results of as-fabricated sandwich structural PZT@C/PU composite damping devices exhibit outstanding vibration attenuating behavior (damping ratio ζ = 0.198). The study herein validates that the carbon shell coated on piezoelectric fillers would effectively increase damping performance of PU-based piezoelectric composites by the enhancement of piezoelectric performance caused by carbon coating piezoelectric fillers, which indicates that this material has potential for future applications in the field of vibration and noise reduction, thereby driving forward and expanding the fundamental understanding in the area of PPCs damping and vibration attenuation.

Ionic liquids (ILs) are a promising class of lubricants that allow dynamic friction control at electrified interfaces. In the real world, surfaces inevitably exhibit some degree of roughness, which can influence lubrication. In this work, we deposited single-layer graphene onto 20 nm silica nanoparticle films to investigate the effect of surface curvature and electrostatic potential on both the lubricious behavior and interfacial layering structure of 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide on graphene. Normal force and friction force measurements were conducted by atomic force microscopy using a sharp silicon tip. Our results reveal that the friction coefficient at the lubricated tip-graphene contacts significantly depends on surface curvature. Two friction coefficients are measured on graphene peaks and valleys with a higher coefficient measured at lower loads (pressures), whereas only one friction coefficient is measured on smooth graphene. Moreover, the electrotunability of the friction coefficient at low loads is observed to be significantly enhanced in peaks and valleys compared with smooth graphene. This is associated with the promoted overscreening of surface charge on convex interfaces and the steric hindrance at concave interfaces, which leads to more layers of ions (electrostatically) bound to the surface, i.e., thicker boundary films (electrical double layers). This work opens new avenues to control IL lubrication on the nanoscale by combining topographic features and an electric field.

Marine biofouling, resulting from the adhesion of marine organisms to ship surfaces, has long been a significant issue in the maritime industry. In this paper, we focused on utilizing soft and hydrophilic hydrogels as a potential approach for antifouling (AF) coatings. Acrylic acid (AA) with a polyelectrolyte effect and N -(3-sulfopropyl)- N -(methacryloxyethyl)- N , N -dimethylammonium betaine (SBMA) with an antipolyelectrolyte effect were selected as monomers. By adjusting the monomer ratio, we were able to create hydrogel coatings that exhibited low swelling ratio in both fresh water and seawater. The Al(OH) 3 nanoparticle, as a physical cross-linker, provided better mechanical properties (higher tensile strength and larger elongation at break) than the chemical cross-linker through the dynamic coordination bonds and plentiful hydrogen bonds. Additionally, we incorporated trehalose into the hydrogel, enabling the repair of the hydrogel network through covalent-like hydrogen bonding. The zwitterion compound SBMA endowed the hydrogel with excellent AF performance. It was found that the highest SBMA content did not lead to the best antibacterial performance, as bacterial adhesion quantity was also influenced by the charge of the hydrogel. The hydrogel with appropriate SBMA content being close to electrical neutrality exhibits the strongest zwitterionic property of PSBMA chains, resulting in the best antibacterial adhesion performance. Furthermore, the pronounced hydrophilicity of SBMA enhanced the lubrication of the hydrogel surface, thereby reducing the friction resistance when applied to the hull surface during ship navigation.

Both the gut microbiome and their host participate in arsenic (As) biotransformation, while their exact roles and mechanisms in vivo remain unclear and unquantified. In this study, as3mt -/- zebrafish were treated with tetracycline (TET, 100 mg/L) and arsenite (iAs III ) exposure for 30 days and treated with probiotic Lactobacillus rhamnosus GG (LGG, 1 × 10 8 cfu/g) and iAs III exposure for 15 days, respectively. Structural equation modeling analysis revealed that the contribution rates of the intestinal microbiome to the total arsenic (tAs) and inorganic As (iAs) metabolism approached 44.0 and 18.4%, respectively. Compared with wild-type, in as3mt -/- zebrafish, microbial richness and structure were more significantly correlated with tAs and iAs, and more differential microbes and microbial metabolic pathways significantly correlated with arsenic metabolites ( P < 0.05). LGG supplement influenced the microbial communities, significantly up-regulated the expressions of genes related to As biotransformation ( gss and gst ) in the liver, down-regulated the expressions of oxidative stress genes ( sod1 , sod2 , and cat ) in the intestine, and increased arsenobetaine concentration ( P < 0.05). Therefore, gut microbiome promotes As transformation and relieves As accumulation, playing more active roles under iAs stress when the host lacks key arsenic detoxification enzymes. LGG can promote As biotransformation and relieve oxidative stress under As exposure.

Multicomponent reactions, particularly the Passerini reaction, serve as efficient tools for the synthesis of druglike molecules and the creation of compound libraries. Despite the effectiveness of the Passerini reaction, the limited alternatives to the crucial carboxylic acid component pose a structural constraint. Here, we have discovered that the phthalimide moiety and its derivatives react in the Passerini reaction as an acid component. We explored their potential in synthesizing diverse and intricate molecules. The phthalimide moiety stands out as a favorable building block due to its oxidative stability, heat-stable characteristics, and resistance to solvents. Our approach introduces a novel perspective to multicomponent reactions by incorporating NH-based acid components, addressing the ongoing need for the development of innovative molecular scaffolds.

Realizing jumping detachment of condensed droplets from solid surfaces at the smallest sizes possible is vital for applications such as antifogging/frosting and heat transfer. For instance, if droplets uniformly jump at sizes smaller than visible light wavelengths of 400-720 nm, antifogging issues could be resolved. In comparison, the smallest droplets experimentally observed so far to jump uniformly were around 16 μm in radius. Here, we show molecular dynamics (MD) simulations of persistent droplet jumping with a uniform radius down to only 3.6 nm on superhydrophobic thin-walled lattice (TWL) nanostructures integrated with superhydrophilic nanospots. The size cutoff is attributed to the preferential cross-lattice coalescence of island droplets. As an application, the MD results exhibit a 10× boost in the heat transfer coefficient (HTC), showing a -1 scaling law with the maximum droplet radius. We provide phase diagrams for jumping and wetting behaviors to guide the design of lattice structures with advanced antidew performance.

Manganese ions (Mn 2+ )-coordinated nanoparticles have emerged as a promising class of antitumor nanotherapeutics, capable of simultaneously disrupting the immunosuppressive tumor microenvironment (TME) and triggering the stimulator of interferon genes (STING) pathway-dependent antitumor immunity. However, the activation of STING signaling by Mn 2+ -based monotherapies is suboptimal for comprehensive stimulation of antigen presenting cells and reversal of immunosuppression in the TME. Here, we report the design of a Mn 2+ /CpG oligodeoxynucleotides (ODNs) codecorated black phosphorus nanosheet (BPNS@Mn 2+ /CpG) platform based on the Mn 2+ modification of BPNS and subsequent adsorption of synthetic CpG ODNs. The coordination of Mn 2+ significantly improved the stability of BPNS and the adsorption of CpG ODNs. The acidic TME and endosomal compartments can disrupt the Mn 2+ coordination, triggering pH-responsive release of CpG ODNs and Mn 2+ to effectively activate the Toll-like receptor 9 and STING pathways. As a result, M2-type macrophages and immature dendritic cells were strongly stimulated in the TME, thereby increasing T lymphocyte infiltration and reversing the immunosuppression within the TME. Phototherapy and chemodynamic therapy, utilizing the BPNS@Mn 2+ /CpG platform, have demonstrated efficacy in inducing immunogenic cell death upon 808 nm laser irradiation. Importantly, the treatment of BPNS@Mn 2+ /CpG with laser irradiation exhibited significant therapeutic efficacy against the irradiated primary tumor and effectively suppressed the growth of nonirradiated distant tumor. Moreover, it induced a robust immune memory, providing long-lasting protection against tumor recurrence. This study demonstrated the enhanced antitumor potency of BPNS@Mn 2+ /CpG in multimodal therapy, and its proof-of-concept application as a metal ion-modified BPNS material for effective DNA/drug delivery and immunotherapy.

Proenzymes, functioning as inactive precursor forms of enzymes, hold significant promise for regulating essential biological processes. Their inherent property of latency, remaining inert until they arrive at the intended site of action, positions them as particularly promising candidates for the development of targeted therapeutics. Despite this potential, the therapeutic potential of proenzymes is challenged by designing proenzymes with excellent selectivity for disease cells. This limitation is further exacerbated by the inability of proenzymes to spontaneously cross the cell membrane, a biological barrier that impedes the cellular internalization of exogenous macromolecules. Therefore, efficacious intracellular delivery is paramount to unlocking the full therapeutic potency of proenzymes.In this Account, we first elucidate our recent advancements made in designing biodegradable lipid nanoparticles (LNPs) for the cell-specific delivery of biomacromolecules, including proteins and nucleic acids. Using a strategy of parallel synthesis, we have constructed an extensive library of ionizable lipids, each integrated with different biodegradable moieties. This combinatorial approach has led to the identification of LNPs that are particularly efficacious for the delivery of biomacromolecules specifically to tumor cells. This innovation capitalizes on the unique intracellular environment of cancer cells to control the degradation of LNPs, thereby ensuring the targeted release of therapeutics within tumor cells. Additionally, we discuss the structure-activity relationship governing the delivery efficacy of these LNPs and their applicability in regulating tumor cell signaling, specifically through the delivery of bacterial effector proteins.In the second segment, we aim to provide an overview of our recent contributions to the field of proenzyme design, where we have chemically tailored proteins to render them responsive to the unique milieu of tumor cells. Specifically, we elaborate on the chemical principles employed to modify proteins and DNAzymes, thereby priming them for activation in the presence of NAD(P)H:quinone oxidoreductase 1 (NQO1), an enzyme that is prevalently upregulated within tumor cells. We summarize the methodologies for intracellular delivery of these proenzymes using biodegradable LNPs, both in vitro and in vivo . The concomitant intracellular delivery and activation of proenzymes are examined in the context of enhanced therapeutic outcomes and targeted CRISPR/Cas9 genome editing.In conclusion, we offer a perspective on the chemical principles that could be leveraged to optimize LNPs for tissue-specific delivery of proenzymes. We also explore chemical strategies for the irreversible modulation of proenzyme activity within living cells and in vivo . Through this discussion, we provide insights into potential avenues for overcoming existing limitations and enhancing the delivery of proenzymes using LNPs, particularly for developing tumor-targeted therapies and genome editing applications.

The sensitive and accurate detection of ochratoxin A (OTA) is crucial for public health due to its high toxicity. Herein, using Au nanoparticle (NP)-attached CdS/UiO-66-NH 2 heterostructures as photoactive materials, a photoelectrochemical (PEC) aptasensor was presented for the ultrasensitive assay of OTA based on a competitive displacement reaction triggering the trans-cleavage ability of CRISPR/Cas12a. In this sensing strategy, methylene blue-labeled single-stranded DNA (MB-ssDNA) was immobilized on the Au NPs/CdS/UiO-66-NH 2 electrode to accelerate the separation of the photogenerated carrier, thus producing a significantly increased PEC response. In the presence of OTA, it specifically bound with the aptamer (Apt) and resulted in the release of the activation chain, triggering the trans-cleavage characteristics of CRISPR/Cas12a. MB-ssDNA was cut randomly on the electrode surface to convert the PEC signal from the "on" to the "off" state, thereby achieving a quantitative and accurate detection of OTA. The CRISPR/Cas12a-derived PEC aptasensor exhibited excellent sensitivity and specificity, with a linear range from 100 to 50 ng/mL and a detection limit of 38 fg/mL. Overall, the proposed aptasensor could provide a rapid, accurate, and sensitive method for the determination of OTA in actual samples.

Conventional photoelectrochemical (PEC) biosensors suffer from the difficulty of visualizing rapid detection and limited accuracy due to a single-signal output. Here, we develop a PEC, electrochromic (EC), and spectral (ST) triple-mode platform for the sensitive visualized detection of nonylphenol (NP). First, the reasonably stepped Fermi energy level arrangement between the defective TiO 2 anode and MoO 3 cathode enables a remarkable photocurrent response (Mode 1). Then, MoO 3 itself is a widely used EC candidate, which can react with free Li-ions to form a Li x MoO 3 intermediate, and its color will change from white to blue accordingly (Mode 2). More importantly, MoO 3 is also a Li-ion host and the potential of Li x MoO 3 depends on the inserted Li-ion quantity deduced by spectral analysis on residual Li-ions in the electrolyte (Mode 3). The EC signal endows fast visual detection, and triple-mode cross-validation improves reliability and accuracy. As a result, this PEC-EC-ST triple-mode molecularly imprinted sensor has a wide linear range (1-5000 μg L -1 ), a low detection limit (0.18 μg L -1 ), selectivity, stability, reproducibility, and actual sample detection capability. This innovative multimode platform not only improves detection reliability but also broadens applications of electrochromic/energy storage materials in biosensors.