Search

The effects of pH, ionic strength, and temperature on sorption of Eu(III) on attapulgite were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The results indicated that the sorption of Eu(III) on attapulgite was strongly dependent on pH and ionic strength, and independent of temperature. In the presence of FA/HA, Eu(III) sorption was enhanced at pH < 4, decreased at pH range of 4-6, and then increased again at pH > 7. The X-ray photoelectron spectroscopy (XPS) analysis suggested that the sorption of Eu(III) might be expressed as ≡ X3Eu0, ≡ SwOHEu3+, and ≡ SOEu—OOC—/HA in the ternary Eu/HN/attapulgite system. The extended X-ray absorption fine structure (EXAFS) analysis of Eu—HA complexes indicated that the distances of d(Eu—O) decreased from 2.415 to 2.360 Å with increasing pH from 1.76 to 9.50, whereas the coordination number (N) decreased from ∼ 9.94 to ∼ 8.56. Different complexation species were also found for the different addition sequences of HA and Eu(III) to attapulgite suspension. The results are important to understand the influence of humic substances on Eu(III) behavior in the natural environment. [ABSTRACT FROM AUTHOR]

To identify the effect of humic acid (HA) and fulvic acid (FA) on the sorption mechanism of Eu(III) on organic-inorganic colloids in the environment at a molecular level, surface adsorbed/complexed Eu(III) on hydrous alumina, HA-, and FA-hydrous alumina hybrids were characterized by using X-ray photoelectron spectroscopy (XPS) and time-resolved laser fluorescence spectroscopy (TRLFS). The experiments were performed in 0.1 mol/L KNO3 or 0.1 mol/L NaCIO4 under ambient conditions. The pH values were varied between 2 and 11 at a fixed Eu(III) concentration of 6.0 × 10-7 mol/L and 4.3 × 10-5 mol/L The different Eu(III)/FA(HA)/hydrous alumina complexes were characterized by their fluorescence emission spectra ((5D0→7F1)/(5D0→1F2)) and binding energy of Eu(III). Inner-sphere surface complexation may contribute mainly to Eu(III) sorption on hydrous alumina, and a ternary surface complex is formed at the HA/FA-hydrous alumina hybrid surfaces. The sorption and species of Eu(III) in ternary Eu-HA/FA-hydrous alumina systems are not dominated by either HA/FA or hydrous alumina, but are dominated by both HA/FA and hydrous alumina. The results are important for understanding the sorption mechanisms and the nature of surface adsorbed Eu(III) species and trivalent chemical homologues of Eu(III) in the natural environment. [ABSTRACT FROM AUTHOR]

Rare-earth-catalyzed annulation reactions using alkenes via C-H activation offer an atom-efficient approach to constructing cyclic compounds. However, the mechanisms underlying these reactions remain poorly understood, limiting the rational design of related catalytic systems. Recently, Hou and Cong reported an unprecedented example of rare-earth-catalyst-controlled diastereodivergent asymmetric [3 + 2] annulation of aromatic aldimines with alkenes. To elucidate the mechanisms and the origins of diastereo- and enantioselectivity, density functional theory calculations were performed. The results revealed that the styrene insertion step determines the stereoselectivity. Styrene insertion follows a similar metal-styrene interaction pattern across different catalysts. Specifically, during cis -insertion, styrene interacts strongly with the metal center, exhibiting significant Sc···Ph interactions, whereas such interactions are absent during trans -insertion. Thus, when the catalyst is employed with a small ligand, stereoselectivity is primarily governed by electronic factors, favoring the cis -insertion mode. In contrast, for the more sterically hindered catalyst, the Sc···Ph interactions in cis -insertion are insufficient to overcome the steric effects, leading to a preference for the trans -insertion mode, which minimizes steric hindrance. These findings offer deeper insights into the origins of catalyst-controlled diastereo- and enantioselectivity and will also contribute to the rational design of stereospecific annulation reactions in rare-earth catalysis.

Controllable and precise delivery of therapeutic agents is critical for effective tumor therapy. However, tumor targeting and the deep penetration of drugs remain among the most challenging issues in achieving controlled delivery. Herein, a novel engineered platelet microneedle patch with a microwave-responsive magnetic biometal-organic framework is proposed to facilitate the combination of the engineered platelet and microwave hyperthermia, enhancing deep drug penetration into tumors and enabling precision therapy. The prepared magnetic biometal-organic framework as nanomedicine exhibits excellent microwave thermal effects. The engineered platelets could be activated in the tumor microenvironment to release PMPs and nanomedicines combined with microwave hyperthermia for enhancing both cell uptake and deep drug penetration into tumors. The developed separable microneedle patch system allows the microneedle tip to be quickly detached from the backing layer and retained within the target tissue for repeated local cancer hyperthermia treatments. By integration of engineered platelets into the microneedle patch, the transdermal deep delivery of drugs could be effectively enhanced for local microwave thermochemotherapy of tumors. This work represents the first attempt to graft microwave-responsive inorganic nanomedicines onto platelets as cell drugs, offering a novel strategy for precise drug delivery activated by microwave thermal therapy.

The side reactions accompanying the charging and discharging process, as well as the difficulty in decomposing the discharge product lithium peroxide, have been important issues in the research field of lithium-oxygen batteries for a long time. Here, single atom Ta supported by Co 3 O 4 hollow sphere was designed and synthesized as a cathode catalyst. The single atom Ta forms an electron transport channel through the Ta-O-Co structure to stabilize octahedral Co sites, forming strong adsorption with reaction intermediates and ultimately forming a film-like lithium peroxide that is highly dispersed. More importantly, the formation of the Ta-O-Co structure can reduce the vacancy formation energy on the catalyst surface, accelerate oxygen activation and conversion into superoxide anions, promote the rapid conversion of strong oxidizing intermediate lithium superoxide into lithium peroxide, avoid the oxidation of lithium superoxide to the electrode and electrolyte, reduce the occurrence of side reactions, and mitigate the production of byproduct lithium carbonate. The overpotential of the battery is reduced significantly, and the reversibility and cycling stability of the battery are improved. This study provides a practical and feasible direction for mitigating the side reaction and improving the performance of the battery.

Accurately identifying new therapeutic uses for drugs is essential to advancing pharmaceutical research and development. Graph inference techniques have shown great promise in predicting drug-disease associations, offering both high convergence accuracy and efficiency. However, most existing methods fail to sufficiently address the issue of numerous missing information in drug-disease association networks. Moreover, existing methods are often constrained by local or single-directional reasoning. To overcome these limitations, we propose a novel approach, truncated arctangent rank minimization and double-strategy neighborhood constraint graph inference (TARMDNGI), for drug-disease association prediction. First, we calculate Gaussian kernel and Laplace kernel similarities for both drugs and diseases, which are then integrated using nonlinear fusion techniques. We introduce a new matrix completion technique, referred to as TARM. TARM takes the adjacency matrix of drug-disease heterogeneous networks as the target matrix and enhances the robustness and formability of the edges of DDA networks by truncated arctangent rank minimization. Additionally, we propose a double-strategy neighborhood constrained graph inference method to predict drug-disease associations. This technique focuses on the neighboring nodes of drugs and diseases, filtering out potential noise from more distant nodes. Furthermore, the DNGI method employs both top-down and bottom-up strategies to infer associations using the entire drug-disease heterogeneous network. The synergy of the dual strategies can enhance the comprehensive processing of complex structures and cross-domain associations in heterogeneous graphs, ensuring that the rich information in the network is fully utilized. Experimental results consistently demonstrate that TARMDNGI outperforms state-of-the-art models across two drug-disease datasets, one lncRNA-disease dataset, and one microbe-disease dataset.

Interferon-γ release assay (IGRA) is one of the most important diagnostic tools for tuberculosis (TB) infection. Despite its high accuracy, conventional IGRA has several drawbacks, including complicated procedures, large blood volume requirements, lengthy incubation times, and difficulties in parallel testing. Efforts have been made to develop miniaturized and highly sensitive biosensors for interferon-γ or to evaluate the specific immune response through microfluidic platforms. However, the need for sophisticated consumables and equipment, as well as the partial experimental design, has limited the application of these advanced techniques in TB diagnosis and disease control. Here, we report the development of a tip optofluidic immunoassay (TOI)-based consolidated microscale IGRA (CM-IGRA) for the dynamic and parallel evaluation of TB infection, refining both the blood incubation and interferon-γ quantification processes. The TOI system comprises 12 microfluidic immuno-reactors and a portable chemiluminescent imaging station, capable of quantifying interferon-γ with high sensitivity (8.00 pg/mL in plasma) and a wide detection range (∼10 4 ). The results generated with CM-IGRA achieved 98.39% agreement with the standard IGRA while reducing blood sample consumption to 50 μL per assay (20-fold reduction) and significantly shortening the incubation time from 20 to 10 h. This diagnostic method simplifies operations and improves efficiency for the parallel assays required in IGRA, providing a promising solution for TB screening in patients for whom current methods are inconvenient, such as children and older adults.

A regioselective [3 + 2] annulation of β,γ-alkynyl-α-ketimino esters with 1,3-dicarbonyls is disclosed. A series of Z -selective dihydrofurans bearing an exocyclic double bond and a quaternary carbon center are accessed without the usage of base. Control and deuterium-labeling experiments have been investigated to probe into the reaction mechanism. The catalyst and base-free nucleophilic addition highlights the transformation.

Solid-phase immunosorbent reactions, such as ELISA, are widely used for detecting, identifying, and quantifying protein markers. However, traditional centimeter scale well-based immunoreactors suffer from low surface-to-volume (S/V) ratios, leading to large sample consumption and a long assay time. Microfluidic technologies, particularly tubular microfluidic immunoreactors, have emerged as promising alternatives due to their high S/V ratios. Despite experimental advancements, multifactor theoretical studies on tubular microfluidic systems are limited. In this study, we present a theoretical model based on the first passage time method to analyze diffusion-controlled reaction kinetics in tubular microfluidic immunoreactors. We focus on key parameters including binding kinetics, reactor size, and solution viscosity. To validate the model, controlled laboratory experiments were conducted using our in-house developed tip optofluidic immunoassay (TOI). These experimental results confirmed the reliability of theoretical models in the behavior prediction of tubular microfluidic systems under real-world conditions. Our model revealed that accurate and rapid protein biomarker quantification requires not only the development of microscale bioreactors but also the design of next-generation probes with extraordinary binding affinity and specificity. This work offers insights into optimizing critical design parameters in future microfluidic immunoassay development, paving ways for next generation microliter-sized biomolecular analysis.

Understanding the interaction between nanomaterials and cellular structures is crucial for nanoparticle applications in biomedicine. We have identified a subtype of stress granules, called nanomaterial-provoked stress granules (NSGs), induced by gold nanorods (AuNRs). These NSGs differ from traditional SGs in their physical properties and biological functions. Uptake of AuNRs causes reactive oxygen species accumulation and protein misfolding in the cell, leading to NSG formation. Physically, NSGs have a gel-like core and a liquid-like shell, influenced positively by HSP70 and negatively by HSP90 and the ubiquitin-proteasome system. AuNRs promote NSG assembly by interacting with G3BP1, reducing the energy needed for liquid-liquid phase separation (LLPS). NSGs impact cellular functions by affecting mRNA surveillance and activating Adenosine 5'-monophosphate (AMP)-activated protein kinase signaling, crucial for a cellular stress response. Our study highlights the role of LLPS in nanomaterial metabolism and suggests NSGs as potential targets for drug delivery strategies, advancing the field of nanomedicine.

Dimension-engineered synthesis of atomically thin II-VI nanoplatelets (NPLs) remains an open challenge. While CdSe NPLs have been made with confinement ranging from 2 to 11 monolayers (ML), CdTe NPLs have been significantly more challenging to synthesize and separate. Here we provide detailed mechanistic insight into the layer-by-layer growth kinetics of the CdTe NPLs. Combining ensemble and single-particle spectroscopic and microscopic tools, our work suggests that beyond 2 ML CdTe NPLs, higher ML structures initially appear as heteroconfined materials with colocalized multilayer structures. In particular, we observe strongly colocalized 3 and 4 ML emissions, accompanied by a broad trap emission. Accompanying transient absorption, single-particle optical, and atomic force microscopy analyses suggest islands of different MLs on the same NPL. To explain the nonstandard nucleation and growth of these heteroconfined structures, we simulated the growth conditions of NPLs and quantified how the monomer binding energy modifies the kinetics and permits single NPLs with multi-ML structures. Our findings suggest that the lower bond energy associated with CdTe relative to CdSe limits higher ML syntheses and explains the observed differences between CdTe and CdSe growth.

For Cu-exchanged zeolite catalysts, Cu 2+ ions existing as Cu 2+ -2Z and [Cu(OH)] + -Z (where Z represents a framework negative charge) are considered the active sites for the selective catalytic reduction of NO x with NH 3 (NH 3 -SCR). Cu 2+ -2Z is more hydrothermally stable and sulfur poisoning-resistant than [Cu(OH)] + -Z. In this work, Cu-CHA and Cu-LTA catalysts containing only Cu 2+ -2Z species were successfully synthesized by a novel impregnation (NIM) method, exhibiting remarkably enhanced hydrothermal stability and sulfur resistance compared with any reported Cu-exchanged zeolite catalysts. It was also found that the [Cu(OH)] + -Z sites can convert to Cu 2+ -2Z by treating at high temperature (850 °C) due to the self-reduction of Cu 2+ to highly mobile Cu + . The use of the NIM method not only significantly simplifies the preparation of the catalysts but also can precisely control the Cu loading, which is very important for the control of Cu species. Many other zeolite catalysts can be prepared by this method.

Glutaminyl cyclases, including glutaminyl-peptide cyclotransferase (QPCT) and glutaminyl-peptide cyclotransferase-like protein (QPCTL), primarily catalyze the cyclization of N-terminal glutamine or glutamate to pyroglutamate (pGlu). QPCTL, in particular, modifies the N-terminus of CD47, thereby regulating its interaction with signal-regulatory protein alpha (SIRPα) and modulating phagocytosis of tumor cells by immune cells. Additionally, QPCTL cyclizes the N-termini of CCL2, CCL7, and CX3CL1, influencing the tumor microenvironment and inflammatory responses in cancer and other disorders. Consequently, QPCTL is considered a valuable therapeutic target for several human diseases. However, the development of QPCTL inhibitors remains in its early stages. This perspective summarizes the structural features, catalytic mechanisms, and biological functions of QPCTL, along with its recent advances in small-molecule inhibitors. It provides valuable insights into the development of novel QPCTL inhibitors.

The electrocatalytic reaction pathway is highly dependent on the intrinsic structure of the catalyst. CO 2 /CO electroreduction has recently emerged as a potential approach for obtaining C 2+ products, but it is challenging to achieve high selectivity for a single C 2+ product. Herein, we develop a Cu atomic ensemble that satisfies the appropriate site distance and coordination environment required for electrocatalytic CO-to-acetate conversion, which shows outstanding overall performance with an acetate Faradaic efficiency of 70.2% with a partial current density of 225 mA cm -2 and a formation rate of 2.1 mmol h -1 cm -2 . Moreover, a single-pass CO conversion rate of 91% and remarkable stability can be also obtained. Detailed experimental and theoretical investigations confirm the significant advantages of the Cu atomic ensembles in optimizing C-C coupling, stabilizing key ketene intermediate (*CCO), and inhibiting the *HOCCOH intermediate, which can switch the CO reduction pathway from the ethanol/ethylene on the conventional metallic Cu site to the acetate on the Cu atomic ensembles.

Pulsed dipolar electron paramagnetic resonance (PD-EPR) measurement is a powerful technique for characterizing the interactions and conformational changes of biomolecules. The extraction of these distance restraints from PD-EPR experiments relies on manipulation of spin-spin pairs. The orthogonal spin labeling approach offers unique advantages by providing multiple distances between different spin-spin pairs. Here, we report an efficient orthogonal labeling approach based on exploiting the cyclization between the 1,2-aminothiol moiety in a protein (e.g., the N-terminal cysteine) with the aldehyde group in a spin label and a thiol substitution (or addition) reaction with a different spin label. We demonstrated that this orthogonal spin labeling method enables high accuracy and precision of multiple protein distance constraints through the PD-EPR measurement from a single sample. This spin labeling approach was applied to characterize the oligomeric state of the trigger factor (TF) protein of Escherichia coli , an important protein chaperone, in solution and cell lysates by distance measurements between different spin-spin pairs. Contrary to popular belief, TF exists mainly in the monomeric state and not as a dimer in the cell lysate.

Cardiac troponin I (cTnI) is a highly sensitive and important serological marker for clinical diagnosis of myocardial injury. Its rapid detection is crucial for the early diagnosis of cardiovascular diseases such as acute myocardial infarction. In this study, based on nucleic acid molecular hybridization and aptamer-specific binding to target molecules, a label-free liquid crystal aptamer sensor based on single-stranded nucleic acid π-structures was developed and applied for the quantitative detection of cTnI. The CP1 and CP2 oligonucleotide chains, complementary to the bases at both ends of the aptamer, are covalently bonded to the sensor substrate via APTES and GA-mediated molecules. The aptamer forms a π-structure with CP1 and CP2 through nucleic acid hybridization, serving as a target molecule capture probe. When cTnI is present in the system, cTnI and the complementary oligonucleotide chains competitively bind with the aptamer, causing the breakdown of the π-structure within the sensor. This reinstates the long-range ordered alignment of the 5CB liquid crystal molecules within the sensor, enabling quantitative measurement of cTnI through variations in optical images. Experimental results show that within the range of 0.01 to 25 ng/mL for cTnI concentration, there is a linear correlation between the brightness area coverage (Br) in the polarized light microscopy images of the sensor and the logarithm of the cTnI concentration, with a correlation coefficient ( r ). The detection limit is 5.16 pg/mL. This method is label-free, simple to operate, and low-cost, with good specificity and a low detection limit, achieving cTnI detection in serum samples.

Recently, significant breakthroughs have been made in the exploration of shale gas in the Lower Cambrian black shale of the Sichuan Basin, indicating a promising commercial extraction potential. However, there remains considerable controversy regarding the pore structural characteristics for this shale formation, especially in the deep-water region. To address this, this paper focused on core samples from two shale gas wells (Xa1 and Xb1) located in the slope-basin facies zone during the Early Cambrian. The analysis involved X-ray diffraction (XRD) analysis, microscopic imaging, and N 2 -CO 2 adsorption-desorption experiments to qualitatively and quantitatively characterize the pore structural characteristics, pore size distribution, and pore types in the deep-water region. The results show that Niutitang shales can be classified into four lithofacies based on mineral composition: siliceous shale, muddy siliceous shale, mixed siliceous shale, and siliceous calcareous shale. Meanwhile, the black shale exhibits diverse pore types, predominantly organic pores, along with significant development of interparticle pores, intraparticle pores, intercrystalline pores, and a few microfractures. In the Niutitang Formation shale of deep-water regions, mesopores contribute the most to the pore volume, followed by macropores, exceeding 89%. Micropores contribute the most to the specific surface area, followed by mesopores, accounting for more than 98%. Each lithofacies shale displays a similar multipeaked distribution pattern, with siliceous shale generally having the most significant pore volume and specific surface area and the highest heterogeneity. Notably, the total organic carbon (TOC) content is the primary factor controlling the micropore structure of the Niutitang Formation shale in the study area, with a less significant impact on mesopores and macropores. Siliceous shale, which has a high average TOC content of 9.58 wt %, exhibits the greatest pore volume and specific surface area. Quartz contributes to the development of micropores in the shale of the study area, whereas clay minerals somewhat inhibit pore development. Overall, the mineral composition has a minor impact on pore development. These findings provide theoretical support for the evaluation of deep shale gas reservoirs and the prediction of favorable areas in the Lower Cambrian Niutitang Formation in Western Hunan., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

One of the important factors leading to lithium dendrites is a slow lithium-ion mass transport and imbalanced distribution of the Li + concentration and nuclei sites on the anode surface. To achieve uniform lithium deposition during the charge and discharge process, we introduce a homemade new copolymer (with the quaternary ammonium group N 3 R + I - on its side chain as the main functional group), named P35, as a functional electrolyte additive to regulate the lithium deposition. Theoretical calculations show that under the strong coordinating interaction between I - and N 3 R + , P35 preferentially adsorbs onto the lithium foil surface, effectively countering the adsorption of lithium salt anions such as PF 6 - . Moreover, the positive charge carried by the quaternary ammonium salt group of P35 could interact with PF 6 - to limit their mobility. Consequently, the dipole interaction on lithium ions is diminished, leading to an enhancement in the transport rate and a decrease in the concentration gradient of lithium ions. Furthermore, a more efficient SEI was formed due to the dual charges electrostatic shield formed by N 3 R + I - . Li-Li symmetric cells and Li-LiFePO 4 full cells assembled with electrolytes with P35 exhibit better rate performance, smaller polarization, and smoother deposition morphology in comparison to the cells without the P35 additive.

Herein, a novel zinc-organic gel with self-catalysis-enhanced electrochemiluminescence (ECL) performance was prepared as an emitter for the first time to assemble a biosensor for ultrasensitive detection of microRNA-221 (miR-221) related to liver cancer. Interestingly, Zn 2+ served as a central ion to coordinate with multidentate ligands 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (TATB) at room temperature to form Zn-TATB-MOGs with excellent ECL intensity. More importantly, compared to metal ions (e.g., Al 3+ , Fe 3+ , and Eu 3+ ) in the reported MOGs with the role of central ions, Zn 2+ in Zn-TATB-MOGs not only served as the central ion but also as a coreaction promoter to facilitate the transformation of S 2 O 8 2- into free radicals SO 4 •- to react with Zn-TATB-MOGs •- for further enhancing the ECL signal of Zn-TATB-MOGs. This was the first time to explore the promotion function of metal ions for coreaction reagents and realize the self-catalysis-enhanced ECL of MOGs. Additionally, the double domino-like cascade strand displacement amplification (DC-SDA) methods could overcome the shortcomings of time-consuming procedures and low DNA utilization in traditional cascade-free amplification methods, which significantly shortened the response time of the biosensor and improved the utilization rate of DNA. Consequently, the constructed biosensor achieved ultrasensitive detection of miR-221 with a detection limit of 2.19 aM, which was lower than reported works. This work provided new insight into broadening the development and improving the performance of MOGs as emitters, holding promise for applications in trace detection of biomarkers and early disease diagnosis.

Developing precious metal-free catalysts for organic reactions under mild conditions is urgent. Herein, we report a three-dimensional covalent organic framework (3D-COF) with high crystallinity and permanent pores, termed 3D-TABPA-COF, for the oxidation of tetrahydroquinoline to quinoline. The 3D-TABPA-COF assembled based on N 4 , N 4 -bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (TABPA) is the catalytic active center for the conversion of tetrahydroquinoline. The triphenylamine in the structure is an effective photosensitizer, which not only enhances the light absorption capacity but also facilitates the rapid transfer of photogenerated electrons and ensures effective carrier separation. The obtained 3D-TABPA-COF has a high specific surface area (2745.06 m 2 g -1 ) and mesopores of 3.57 nm. This is attributed to the fact that the bor topology is not easy to interpenetrate. It can oxidize tetrahydroquinoline to obtain quinoline efficiently under visible light irradiation. In addition, we also performed various photochemical characterizations combined with density functional theory calculations to elucidate the reaction mechanism from tetrahydroquinoline to quinoline. This work provides a feasible strategy for constructing 3D-COF to achieve efficient photocatalytic organic reactions.

Single-crystalline Ni-rich layered oxides are one of the most promising cathode materials for lithium-ion batteries due to their superior structural stability. However, sluggish lithium-ion diffusion kinetics and interfacial issues hinder their practical applications. These issues intensify with increasing Ni content in the ultrahigh-Ni regime (≥90%), significantly threatening the practical viability of the single-crystalline strategy for ultrahigh-Ni layered oxide cathodes. Herein, by developing a high-entropy coating strategy, we successfully constructed an epitaxial lattice-coherent high-entropy rock-salt layer (∼3 nm) via Zr and Al doping on the surface of the single-crystalline cathode LiNi 0.92 Co 0.05 Mn 0.03 O 2 through an in situ modification process. The surface high-entropy rock-salt layer with tailored Ni valence and lattice coherence not only greatly improves lithium-ion diffusion kinetics but also suppresses interface parasitic reactions and surface structural degradations. The high-entropy surface layer-stabilized ultrahigh-Ni single-crystalline cathode (SC-Ni92-ZA) demonstrates significantly improved rate and cycling performances (127.5 mAh g -1 at 20C, capacity retention of 74.9% after 500 cycles at 1C) in a half-cell. The SC-Ni92-ZA exhibits a capacity retention of 87.1% after 600 cycles at 1C in a full-cell. This epitaxial lattice-coherent high-entropy coating strategy develops a promising avenue for developing high-capacity, long-life cathode materials.

The efficacy of immunotherapy in treating triple-negative breast cancer (TNBC) has been restricted due to its low immunogenicity and suppressive immune microenvironment. Bacterial outer membrane vesicles (OMVs) have emerged as innovative immunotherapeutic agents in antitumor therapy by stimulating the innate immune system, but intricate modifications and undesirable multiple dose administration severely hinder their utility. Herein, a two-step bacterial metabolic labeling technique was utilized for the bioorthogonal engineering of OMVs. At first, d-propargylglycine (DPG, an alkyne-containing d-amino acid) was introduced into the incubation process of probiotic Escherichia coli 1917 (Ecn) to produce DPG-functionalized OMVs, which were subsequently conjugated with azide-functionalized new indocyanine green (IR820) to yield OMV-DPG-IR820. The combination of phototherapy and immunostimulation of OMV-DPG-IR820 effectively arouses adaptive immune responses, causing maturation of dendritic cells, infiltration of T cells, repolarization of the M2 macrophage to the M1 macrophage, and upregulation of inflammatory factors. Remarkably, OMV-DPG-IR820 demonstrated tumor-targeting capabilities with guidance provided by near-infrared II (NIR-II) fluorescence imaging, leading to remarkable inhibition on both primary and distant tumors and preventing metastasis without causing noticeable adverse reactions. This study elucidates a sophisticated bioorthogonal engineering strategy for the design and production of functionalized OMVs and provides novel perspectives on the microbiome-mediated reversal of TNBC through a precise and efficient immunotherapy.

Enhancing the hydrophobic and photothermal characteristics of the coating can significantly boost its anti-icing/ice-melting capabilities. In this study, an epoxy resin thermal insulation layer is interposed between the aluminum sheet substrate and the C/TiN/WC/PDMS photothermal composite coating. This method not only equips the coating with exceptional superhydrophobic properties but also markedly elevates its photothermal and anti-icing/ice-melting performance. The incorporation of the thermal insulation layer has been observed to elevate the water contact angle from approximately 125° to 155° ± 0.5° while simultaneously reducing the water sliding angle from over 90° to about 4° ± 0.5°. In an environmental setting of -15 °C and 65% ± 5% humidity, under irradiation of 1.0, 0.7, 0.5, and 0.3 kW/m 2 , the coating with the thermal insulation layer exhibited saturation temperature increments of roughly 4.7, 3.4, 5.4, and 4.6 °C, respectively, compared to the photothermal coating without the insulation layer. In the absence of irradiation, the coating with the insulation layer delayed the freezing time of 80 μL water droplets by up to three and six times compared to the coating without an insulation layer and the bare aluminum sheet substrate, respectively. Furthermore, under 0.3 kW/m 2 irradiation, the coating with the insulation layer reduced the initial melting time and complete melting time of ice beads by nearly half and one-third, respectively, whereas the ice beads on the aluminum sheet substrate remained unmelted throughout the observation period.

An innovative and potent nanozyme with reductase-like activity was developed by integrating the in situ synthesis of gold nanoparticles (Au NPs) onto the surface of a covalent organic framework (COF). Based on the reductase-like activity of the COF-hybridized Au NPs, this nanozyme could efficiently catalyze the reduction of 4-nitrophenol (4-NPH). Moreover, the prepared nanohybrid was utilized as an excellent surface-enhanced Raman scattering (SERS) substrate for highly sensitive SERS detection by combining the excellent adsorption properties of COFs and the large number of Raman hotspots between the high-density Au NPs. For the first time, 4-NPH was used as an SERS marker to detect the electron receptor acetylcholine (Ach), with high sensitivity; Ach acted as an inhibitor in this catalytic reaction. The linear range of Ach was 1.0 pM to 10 nM, the correlation coefficient was 0.993, the detection limit was approximately 0.3 pM with a signal-to-noise ratio (s/n) of 3, and the acceptable recovery in the serum was 97.2% to 104.5%. The results from this study show that the nanozyme-SERS system has great potential for chemical and bioassay applications.

In this study, we developed a flexible, biocompatible, and high-output electrical performance triboelectric nanogenerator (TENG) employing a silk fibroin (SF)-MXene composite film (SF-MXene-F) and a PDMS film as the friction layer. The inclusion of MXene in the SF film increased its surface charge density, presenting a practical approach to designing high-performance SF composite film-based TENGs. At a MXene content of 40%, our SF-MXene composite film-based TENG (SF-MXene-FTENG) achieved optimal output electrical performance, featuring a maximum open-circuit voltage (Voc) of 418 V, a maximum short-circuit current (Isc) of 11.6 μA, and a maximum output power density of 9.92 W/m 2 . The Voc and power densities of the SF-MXene-FTENG surpassed previously reported optimal values for SF-based TENGs by 1.6 and 3.8 times, respectively. Furthermore, leveraging the exceptional biocompatibility and light shading performance of TENGs, we designed a wearable smart TENG eye mask capable of diagnosing insomnia symptoms and monitoring sleep quality in real time. The SF-MXene-FTENG holds promising application potential as a wearable electronic device for diagnosing sleep-related diseases.

Using chemical fungicides is the main strategy for controlling potato late blight (PLB), a devastating pre- and postharvest disease caused by Phytophthora infestans , resulting in environmental pollution and health risks. It is of great importance to develop a biofungicide from microorganisms. Through isolating potato rhizosphere microorganisms, CQUSh011 was found to have antioomycete activity with strong inhibition on vegetative growth and virulence of P. infestans . Morphological and molecular identification indicated that CQUSh011 belongs to Streptomyces rapamycinicus . Based on genome, metabolome, and HPLC quantification, rapamycin and salicylic acid were found to be the two active metabolites against P. infestans . Continuous field trials showed that CQUSh011 has sustainable control efficiency against PLB, and the efficiency was better when combined with Infinito, along with an increased endophytic microbial community and biodiversity in potato roots. The results demonstrated the potential of CQUSh011 as a biofungicide against PLB and provided an alternative strategy for reducing the application of chemical fungicides.

Triple-negative breast cancer (TNBC) is highly heterogeneous, lacks accessible therapeutic targets, and features an immunosuppressive tumor microenvironment (TME). Anthracycline-based chemotherapy remains the primary treatment method for TNBC, while the current popular immune checkpoint inhibitors persistently encounter therapeutic resistance. Therefore, there is an urgent need to explore combined therapeutic strategies to remodel the TME and improve the treatment response. Considering the highly specific homing ability of tumor cell-derived vesicles and the key role of the signal transduction and activation of the transcription factor 3 (STAT3) pathway in TNBC, we propose a synergistic therapeutic strategy that integrates gene therapy, chemotherapy, and immunotherapy based on STAT3 short interfering RNA (siSTAT3) and doxorubicin (DOX)-functionalized tumor-derived extracellular vesicles (TEVs) (siSTAT3-DOX@TEV). The in vitro and in vivo results demonstrate that siSTAT3-DOX@TEV target tumor tissues precisely, downregulate STAT3 expression, and synergistically and efficiently induce immunogenic death, thereby reversing the immunosuppressive TME. Moreover, mass cytometry and immunohistochemistry reveal the local immune activation effect of siSTAT3-DOX@TEV, with a significant increase in M1 macrophages, CD4 + T cells, and CD8 + T cells in tumor tissues. These results provide strong hints for the development of TEV-based chemo-gene therapeutic agents for TNBC treatment at the clinical level.

Reactive sulfur species (RSS) including persulfides (RSSHs), biothiols, and hydrogen sulfide (H 2 S) are key regulators in various physiological processes. To better understand the symbiotic relationship and interconversion of these RSS, it is highly desirable but challenging to develop analytical techniques that are capable of detecting and quantifying them. Herein, we report the rational design and synthesis of novel trityl-radical-based electron paramagnetic resonance (EPR) probes dubbed CT02-TNB and OX-TNB. CT02-TNB underwent fast sulfur exchange reactions with two reactive RSSHs (PS1 and PS2) which were released from their corresponding donors PSD1 and PSD2 to afford the specific conjugates. The resulting conjugates exhibit characteristic EPR spectra, thus enabling discriminative detection and quantitation of the two RSSHs. Moreover, CT02-TNB showed good response toward other RSS including glutathione (GSH), cysteine (Cys), H 2 S, and sulfite as well. Importantly, based on the updated EPR spectral simulation program, simultaneous quantitation of multiple RSS (e.g., PS1/GSH/Cys or PS1/GSH/H 2 S) by CT02-TNB was also achieved. Finally, the levels of released PS1 from PSD1 and endogenous GSH in isolated mouse livers were measured by the hydrophilic OX-TNB. This work represents the first study achieving discriminative and quantitative detection of different persulfides and other RSS by a spectroscopic method.

We disclose herein an efficient and facile method for the synthesis of SF 5 -containing isoquinolinediones with an all-carbon quaternary stereocenter via intramolecular pentafluorosulfanylation of acrylamides using SF 5 Cl as a pentafluorosulfanylation reagent. The protocol proceeds under mild reaction conditions and enjoys a broad substrate scope, wide functional group compatibility, and high atom- and step-economy. A radical mechanism involving the SF 5 radical cascade addition/cyclization of acrylamides is proposed.

The inevitable dealumination process of zeolite Y is closely related to ultrastabilization, enhanced Bro̷nsted acidity, and deactivation throughout its life cycle, producing complex aluminum and acidic hydroxyl species. Most investigations on dehydrated zeolites have focused on the Bro̷nsted acidity of tetra-coordinated Al (Al(IV)) and Lewis acidity associated with tricoordinated Al (Al(III)) sites, which has left the penta-coordinated Al (Al(V)) in dealuminated zeolites scarcely discussed. This is largely due to the oversimplified view of detectable Al(V) as an exclusively extra-framework species with Lewis acidity. Here we report the formation of Bro̷nsted acidic penta-coordinated Al species (Al(V)-BAS) in the dealumination process. Two-dimensional (2D) through-bond and multiquantum 1 H-{ 27 Al} correlation solid-state NMR experiments demonstrate the presence of a bridging Si-OH-Al(V) structure in dealuminated Y zeolites. Different from the conventional belief that water attack leads to the breaking of zeolite framework Al-O bonds in the initial stage of zeolite dealumination, the observed Al(V) as a dealumination intermediate is directly correlated with a BAS pair because of the direct dissociation of water on the framework tetrahedral aluminum (Al(IV)), thus bypassing the cleavage of Al-O bonds. 1 H double-quantum solid-state NMR experiments and theoretical calculations provide further evidence for this mechanism, whereas pyridine adsorption experiments confirm stronger acidity of Al(V)-BASs than the traditional bridging hydroxyl groups associated with Al(IV). We were also able to detect the Al(V)-BAS site from dealuminated SSZ-13 zeolite with CHA topology, suggesting that its creation is not specific to the framework structure of zeolites.

Transition metal-catalyzed spiroannulations are practical strategies for constructing spirocyclic skeletons of pharmaceutical and biological significance, yet the microscopic mechanism still lacks in-depth explorations. Here, the palladium-catalyzed [2 + 2 + 1] spiroannulation between aryl halides and alkynes was studied by employing the density functional theory (DFT) method. Based on comprehensive explorations on a couple of possible reaction pathways, it is found that the reaction probably experiences C-I oxidative addition, alkyne migration insertion, Cs 2 CO 3 -assisted aryl C-H activation, C-Br bond oxidative addition, C-C coupling, arene dearomatization and reductive elimination in sequence and leads to the formation of the spiro[4,5]decane pentacyclic product ( P ) ultimately. Among these, the C-Br bond oxidative addition step acts as the rate-determining step (RDS) of the whole reaction, featuring a practical free energy barrier of 32.4 kcal·mol -1 at 130 °C. Computationally predicted kinetics such as half-life transferred from the RDS step's barrier on the optimal reaction pathway (1.2 × 10 1 h) coincides well with corresponding experimental results (91% yield of the spiro[4,5]decane pentacyclic product P after reacting 10 h at 130 °C). In addition, theoretical predictions regarding the solvent/ligand effects and base additive role in the reaction, rationalized by distortion-interaction/natural population/noncovalent interaction analyses, are also in good agreement with experimental data and trend. This good agreement between experiment and theory makes sense for new designations and further experimental improvements of such Pd-catalyzed transformations.

A novel and efficient palladium-catalyzed highly regioselective reaction of 1-[2-(2,2-dibromoethenyl)phenyl]-1 H -pyrrole with allenes was realized to synthesize pyrrolo[1,2- a ]quinolones. The tandem process involves intermolecular cyclization and intramolecular direct arylation, leading to the formation three new C-C bonds and two new rings. Notably, this transformation exhibits broad substrate scope and high functional group tolerance.

Without intervention, the natural wound healing process can often result in scarring, which can have detrimental effects on both the physical and mental well-being of patients. Therefore, it is crucial to develop biomaterials that can promote healing without scarring. Regulating the Yes-associated protein-1/PDZ-binding motif (YAP/TAZ) signaling pathway is possible to reduce excessive fibrosis of fibroblasts and proliferation of vascular endothelial cells, ultimately impacting scar formation. Arsenic trioxide (ATO), an ancient drug with medicinal and toxic properties, has shown promise in regulating this pathway. An ATO-loaded hydrogel dressing (ATO@CS/SA) was created to facilitate scarless wound healing, utilizing chitosan (CS) and sodium alginate (SA) to prevent direct contact of ATO with the wound tissue and minimize potential side effects. In vitro studies demonstrated that low concentrations of ATO did not impact cell viability and even promoted proliferation and migration. Co-culturing the hydrogel with fibroblasts and vascular endothelial cells led to decreased expression levels of YAP and TAZ. Animal studies over a 90-day period revealed significant inhibition of scar formation with this system. Histological experiments further confirmed that the decreased expression of YAP and TAZ was responsible for this outcome. In conclusion, when administered at the appropriate dose, ATO can be repurposed from a traditional poison to a therapeutic agent, effectively suppressing excessive cell fibrosis and blood vessel proliferation and offering a novel approach to scar-free treatment.

Larock isoquinoline synthesis is one of the most efficient and straightforward approaches to the construction of 3,4-disubstituted isoquinolines. However, there have been no asymmetric versions for the synthesis of axially chiral isoquinolines since their initial report in 2001. Herein, we documented the first example of an asymmetric Larock isoquinoline synthesis by employing Pd(OAc) 2 /Walphos SL-W002-1 as the catalyst, affording the axially chiral 3,4-disubstituted isoquinolines with up to 97.5:2.5 er and 98% yield. Density Functional Theory (DFT) calculations clearly clarified the catalytic mechanism and the origin of the experimentally observed enantioselectivity.

Emission trading schemes (ETS) are increasingly becoming a popular policy instrument to balance carbon abatement and economic growth. As a globally unified carbon pricing system has not yet been established, whether regionally operated ETSs cause carbon leakage remains a major concern. Taking China's regional pilot ETSs as a quasi-natural experiment, the study uses the spatial difference-in-differences method to examine how regional ETSs affect carbon emissions in and outside cities of policy implementation. Our analysis finds that China's regional ETS policy contributes to a 6.1% reduction in urban CO 2 emissions and a 6.6% decline in emissions intensity in regulated cities, causing carbon leakages that increase CO 2 emissions in neighboring cities by 1.7% on average. Our finding further suggests that regional ETSs mitigate local CO 2 emissions through outsourcing production, improving energy efficiency and decarbonizing energy structure, whereas the outsourcing of industrial production drives up CO 2 emissions in adjacent cities. Moreover, the performances of regional ETSs vary largely by socioeconomic context and mechanism design. China's regional ETSs reduce CO 2 emissions more effectively in central and industrial cities but with more severe carbon leakage, while rigorous compliance mechanisms and active market trading help deepen carbon abatement and alleviate carbon leakage.

4-Quinolone derivatives undergo an unexpected ring expansion reaction with α-halo esters/phosphonates/sulfones in the presence of a base, such as NaH, to produce novel benzazepinones. Under these mild and transition-metal-free conditions, most substrates gave moderate to excellent yields. The reaction could be applied in gram-scale synthesis of drug-like molecules that greatly accelerated our structure-activity relationship studies. A plausible mechanism was proposed.

Formation of new chemical species has been achieved under an electric field by the use of the scanning tunneling microscope break junction technique, yet simultaneous implementation of catalytic reactions both at the organic/metal interface and in the bulk solution remains a challenging task. Herein, we show that n -butyl-substituted organotin-terminated benzene undergoes both an efficient cleavage of the terminal tributyltin group to form a covalent Au-C bond and a homocoupling reaction to yield biphenyl product when subjected to an electric field in the vicinity to Au electrodes. By using ex situ characterization of high-performance liquid chromatography with an UV-vis detector, we demonstrate that the homocoupling reaction can occur with high efficiency under an extremely low tip bias voltage of ∼5 mV. Additionally, we show that the efficiency of the homocoupling reaction varies significantly in different solvents; the choice of the solvent proves to be one of the methods for modulating this reaction. By synthesizing and testing varied molecular backbone structures, we show that an extended biphenyl backbone undergoes homocoupling to form a quarterphenylene backbone, and the C-C coupling reactions are prohibited when additional aurophilic or bulky chemical groups that exhibit a steric blockage are introduced.

Holographic data storage technology is a cost-effective solution for long-term archival data storage. However, the development of suitable holographic recording materials remains a challenge. Among these materials, phenanthraquinone-doped poly(methyl methacrylate) (PQ/PMMA) stands out due to its low cost and controllable thickness. Nevertheless, its limited photosensitivity and diffraction efficiency hinder its widespread application. In order to solve these problems, we put forward a kind of convenient and simple, low cost strategy, by adding plasticizer N , N -dimethylformamide (DMF) for preparation of DMF-PQ/PMMA photopolymer, avoid the use of complex compounds. The addition of DMF not only influences the thermal polymerization stage but also forms weak interactions with PQ during the photoreaction process, thereby enhancing the holographic performance of DMF-PQ/PMMA. Consequently, we achieved a remarkable 9.1-fold increase in photosensitivity (from ∼0.35 to 3.18 cm J -1 ), improved diffraction efficiency by 20% (from 65% to 80%), and reduced volume shrinkage by a factor of 8 (from 0.4% to 0.05%). Furthermore, utilizing a collinear holographic storage system with multiplexing shift at a scale of 5 μm resulted in an impressively low minimum bit error rate (BER) of only 0.36% (with an average BER of 1.4%), highlighting the fast processing capability and potential for low BER applications in holographic information storage using DMF-PQ/PMMA.

Iron-nitrogen-carbon (Fe-N-C) materials have been identified as a promising class of platinum (Pt)-free catalysts for the oxygen reduction reaction (ORR). However, the dissolution and oxidation of Fe atoms severely restrict their long-term stability and performance. Modulating the active microstructure of Fe-N-C is a feasible strategy to enhance the ORR activity and stability. Compared with common 3d transition metals (Co, Ni, etc.), the 4d transition metal atom Nb has fewer d electrons and more unoccupied orbitals, which could potentially forge a more robust interaction with the Fe site to optimize the binding energy of the oxygen-containing intermediates while maintaining stability. Herein, an asymmetric Fe-Nb diatomic site catalyst (FeNb/c-SNC) was synthesized, which exhibited superior ORR performance and stability compared with those of Fe single-atom catalysts (SACs). The strong interaction within the Fe-Nb diatomic sites optimized the desorption energy of key intermediates (*OH), so that the adsorption energy of Fe-*OH approaches the apex of the volcano plot, thus exhibiting optimal ORR activity. More importantly, introducing Nb atoms could effectively strengthen the Fe-N bonding and suppress Fe demetalation, causing an outstanding stability. The zinc-air battery (ZAB) and hydroxide exchange membrane fuel cell (HEMFC) equipped with our FeNb/c-SNC could deliver high peak power densities of 314 mW cm -2 and 1.18 W cm -2 , respectively. Notably, the stable operation time for ZAB and HEMFC increased by 9.1 and 5.8 times compared to Fe SACs, respectively. This research offers further insights into developing stable Fe-based atomic-level catalytic materials for the energy conversion process.

Stable magnetic core-shell nanostructures are developed by lattice locking lanthanide-iron (La-Fe) oxide shells with magnetite cores to prevent the release of La from the surfaces of the magnetite nanostructures. The resulting core-shell nanostructures demonstrate excellent outstanding regeneration performance and high adsorption capacity for phosphate (115 mg P·g -1 ). These nanostructures release minimal La from the magnetite core surfaces after adsorbent regeneration, with a La loss of only 20% compared to the control sample, Mag@La(OH) 3 . La 3+ ions were released at concentrations ranging from 1 to 2.3 μg·L -1 at pH levels of 4 to 8, which is within the metal content range found in natural aquatic environments. These results demonstrate the high stability of the nanostructures after regeneration. Furthermore, the adsorbent exhibits high extraction capacity across a wide pH range of 4 to 10 and performs well even in the presence of interfering anions at phosphate-to-anion molar ratios of 1:5, 1:25, and 1:100. Microscopic and spectroscopic analyses reveal that the primary extraction mechanism of phosphate in the La-containing shells is surface precipitation. This approach not only improves the use of magnetic core-shell nanostructures as adsorbents but also demonstrates the creation of a broad range of stable magnetic functional materials for diverse applications.

Ion preintercalation is an effective method for fine-tuning the electrochemical characteristics of electrode materials, thereby enhancing the performance of aqueous ammonium-ion hybrid supercapacitors (A-HSCs). However, much of the current research on ion preintercalation lacks controllability, and the underlying mechanisms remain unclear. In this study, we employ a two-step electrochemical activation approach, involving galvanostatic charge-discharge and cyclic voltammetry, to modulate the preintercalation of NH 4 + in MnO 2 . An in-depth analysis of the electrochemical activation mechanism is presented. This two-step electrochemical activation approach endows the final MnO 2 /AC electrode with a high capacitance of 917.4 F g -1 , approximately 2.4 times higher than that of original MnO 2 . Furthermore, the MnO 2 /AC electrode retains approximately 93.4% of its capacitance after 10 000 cycles at a current density of 25 mA cm -2 . Additionally, aqueous A-HSC, comprising MnO 2 /AC and P-MoO 3 , achieves a maximum energy density of 87.6 Wh kg -1 . This study offers novel insights into the controllable ion preintercalation approach via electrochemical activation.

Electrocatalytic coupling of CO 2 and NO 3 - to urea is a promising way to mitigate greenhouse gas emissions, reduce waste from industrial processes, and store renewable energy. However, the poor selectivity and activity limit its application due to the multistep process involving diverse reactants and reactions. Herein, we report the first work to design heterostructured Cu-Bi bimetallic catalysts for urea electrosynthesis. A high urea Faradaic efficiency (FE) of 23.5% with a production rate of 2180.3 μg h -1 mg cat -1 was achieved in H-cells, which surpassed most reported electrocatalysts in the literature. Moreover, the catalyst had a remarkable recycling stability. Experiments and density functional theory calculations demonstrated that introduction of moderate Bi induced the formation of the Bi-Cu/O-Bi/Cu 2 O heterostructure with abundant phase boundaries, which are beneficial for NO 3 - , CO 2 , and H 2 O activation and enhance C-N coupling and promote *HONCON intermediate formation. Moreover, favorable *HNCONH 2 protonation and urea desorption processes were also validated, further explaining the reason for high activity and selectivity toward urea.

Convenient and accurate quantification of disease-relevant multitargets is essential for community disease screening. However, in the field of photoelectrochemical (PEC) sensors for multisubstance detection, research on the continuous detection of multiple targets using a polarity-switching mode is scarce. In this study, a multiplexed PEC bioassay was developed based on a target-triggered "anodic-cathodic-anodic" multiple-polarity-switchable mode. Employing miRNA-21 and miRNA-141 as model analytes, the photosensitive material combinations of Cu 2 O/gold nanoparticles (AuNPs)/TiO 2 and CdS/AuNPs/TiO 2 were successively formed through the specific binding of different whisker branches of Whisker-DNA to Cu 2 O-H1 and the CdS-tripod DNA ring, respectively. This process reverses the photocurrent polarity from anodic to cathodic and then back to anodic upon detecting different targets, resulting in the high-sensitivity quantification of various biological targets with reduced interference. To enhance the device's utility and affordability in community disease screening, integrating a capacitor and a multimeter-smartphone connection simplifies the assembly and reduces costs. In developing the PEC sensor, the device demonstrated linear detection ranges for miRNA-21 and miRNA-141 from 0.01 fM to 10 nM. Detection limits for miRNA-21 and miRNA-141 were established at 3.2 and 4.3 aM, respectively. The innovative target-triggered multiple-polarity-switchable mode offers adaptability for other multitarget detections by simply modifying the structure of the whisker branches and the combination of photosensitive materials.

Acute alcoholic liver injury (AALI) has become an important cause of liver disease worldwide, and there is an urgent need to develop noninvasive and sensitive methods to detect and evaluate AALI. We report herein three novel but readily available mitochondrial targeting fluorescence probes ( ICR , ICJ , and ICQ ) for AALI detection. These probes contain different electron-donating groups, among which ICQ exhibits NIR fluorescence (740 nm), a large Stokes shift (110 nm), and a sensitive response to viscosity (73-fold enhancement in fluorescence from water to glycerol), making it suitable for in vivo imaging. ICQ also exhibits an excellent ability to image mitochondrial viscosity changes in cells. More importantly, ICQ can target the liver selectively and image the viscosity changes in the liver noninvasively. Through establishing an AALI mouse model, ICQ was successfully applied to the in situ imaging changes in liver viscosity during the AALI process. The results showed a significant increase in liver viscosity in AALI mice, indicating that viscosity can serve as a marker for AALI, and ICQ is a promising noninvasive and sensitive tool for detecting and evaluating AALI.

Atmospheric water harvesting has attracted much attention because of its potential to escalate the global freshwater shortage. However, the water collection efficiency is hindered by the trade-off between fast droplet nucleating and rapid droplet dripping due to the opposite requirements in the chemistry and the morphology of surfaces. Herein, the hierarchical porous composite film (ZIF-8@PVDF/PMMA, HPCF) with superhydrophobicity is designed for highly efficient and stable water harvesting. It indicates that the HPCF film has a large water contact angle (WCA) of 155.50° and ultralow sliding angle (SA) of 2°, exhibiting the self-cleaning function. Significantly, it is demonstrated that the water collection efficiency of HPCF can achieve 1.13 g·cm -2 ·h -1 , which is much higher than the value of the blank sample, as well as most of the reported values. It is attributed to the hierarchical porous structure with the ZIF-8 crystals enhancing the surface roughness and endowing the film with the hydrophilic/superhydrophobic regions. This design promotes an optimal balance between droplet nucleation and shedding, significantly enhancing the water harvesting efficiency. Consequently, this work introduces an effective approach for water collection materials suitable for fog/mist conditions and provides an effective solution for the foggy area with water scarcity, demonstrating significance for advancing research aimed at mitigating the worldwide water shortage.

Preventing microbial infections and accelerating wound closure are essential in the process of wound healing. In this study, various concentrations of carvacrol (CA) were loaded into polyacrylonitrile/poly(ethylene oxide) (PAN/PEO) nanofiber membranes to develop potential wound dressing materials via an electrospinning technique. The morphology and structure of the PAN/PEO/CA nanofiber membrane were analyzed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. Subsequently, antimicrobial performance testing showed that the PAN/PEO/CA nanofiber membrane exhibited antimicrobial activity in a concentration-dependent manner. Moreover, SEM and transmission electron microscopy revealed that the number of Staphylococcus aureus decreased significantly and the microstructure of the biofilm was seriously damaged. Next, compared with the control and PAN/PEO groups, the PAN/PEO/5% CA group in a full-thickness skin infection model not only exhibited reduced wound exudate on day 2 after infection but also displayed a greater ability to achieve complete skin regeneration, with faster wound healing. Finally, the Kyoto Encyclopedia of Genes and Genomes pathway analysis revealed that the downregulated differentially expressed genes between PAN/PEO- and PAN/PEO/5% CA-treated S. aureus were enriched in the two-component system and S. aureus infection. In conclusion, the antimicrobial materials of PAN/PEO/CA inhibited microbial growth and promoted wound healing with potential applications in the clinical management of wounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)