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Results of an exhaustive experimental study of the valence electronic structure of thiophene using high resolution electron momentum spectroscopy at impact energies of 1200 and 2400 eV are presented. The measurements were performed using an electron momentum spectrometer of the third generation at Tsinghua University, which enables energy, polar and azimuthal angular resolutions of the order of E0.8 eV, ±0.53° and ±0.84°. These measurements were interpreted by comparison with Green's function calculations of one-electron and shake-up ionization energies as well as of the related Dyson orbital electron momentum distributions, using the so-called third-order algebraic diagrammatic construction scheme (ADC(3)). Comparison of spherically averaged theoretical electron momentum distributions with experimental results very convincingly confirms the presence of two rather intense -21shake-up lines at electron binding energies of 13.8 and 15.5 eV, with pole strengths equal to 0.18 and 0.13, respectively. Analysis of the electron momentum distributions associated with the two lowest 2A2(3-1) and 2B1(2-1) cationic states provides indirect evidence for a symmetry lowering and nuclear dynamical effects due to vibronic coupling interactions between these two states. ADC(3) Dyson orbital momentum distributions are systematically compared with distributions derived from Kohn−Sham (B3LYP) orbitals, and found to provide most generally superior insights into experiment. [ABSTRACT FROM AUTHOR]

Reactive nitrogen (Nr) emissions significantly affect air quality and the nitrogen cycle in ecosystems. Heavy-duty diesel vehicles (HDDVs), as major sources of these emissions, exhibit complex emission characteristics because of the combined effects of different driving conditions and aftertreatment technologies. This study first investigated the emission factors (EFs) of Nr species, including NO, NO 2 , HONO, N 2 O, and NH 3 , from HDDVs under different emission standards (China IV/V/VI) and cheating strategies, with a particular focus on the impact of selective catalytic reduction (SCR) systems. Vehicles employing water injection cheating present NO, NO 2 , and HONO EFs that are consistent with the China III standards, significantly undermining the effectiveness of Nr emission control. The evolution of SCR technology in China IV, V, and VI standards has generally led to substantial reductions in NO, NO 2 , and HONO emissions, yet the integration of ammonia slip catalysts (ASC) systems in China VI vehicles presents new challenges. While ASCs have successfully reduced NH 3 slip to an average of 17 ± 12 mg/km, they have also caused a 6-13-fold increase in N 2 O emissions compared with those of China IV and V vehicles, reaching levels of 205 ± 85 mg/km. Additionally, China VI vehicles exhibit a marked increase in the HONO/NOx ratio, which increases from 0.9% in China V to 4.6%. These increases are attributed to high-temperature oxidation of NH 3 within the ASC catalyst, leading to undesirable byproducts. The temporal dynamics of Nr emissions under real-world driving conditions further reveal that the effectiveness of aftertreatment technologies and their selectivity toward byproducts vary depending on the driving mode. This variability underscores the need for further optimization of the SCR and ASC technologies to balance the control of all the reactive nitrogen species effectively.

BiVO 4 is a stable photocatalytic material but has poor photocatalytic activity in visible light. Herein, the surfactants were investigated to enhance the photocatalytic degradation of tetracycline (TC) of BiVO 4 through a hydrothermal method. The different molecular structures and properties of surfactant-modified BiVO 4 show clustered small spheres and stacked plate-like microcrystals. The N -hexadecyltrimethylammonium chloride (CTAC)-modified BiVO 4 (BiVO 4 -CTAC) with stacked plate-like morphology increases the light absorption range and decreases the energy band gap. Surfactants with different hydrophilic groups and molecular structures affect the formation process of BiVO 4 , regulating the morphology, crystal structure, and crystalline surface exposure of BiVO 4 . BiVO 4 -CTAC has demonstrated superior TC degradation efficiency compared with the original BiVO 4 (BiVO 4 -Blank). This enhancement is attributed to the observation in the Nyquist plot, where BiVO 4 -CTAC exhibits the smallest arc radius, indicative of reduced charge transfer resistance and improved charge separation. Furthermore, holes (h + ) and superoxide radicals ( • O 2 - ) reactive species are the main active radicals for TC photocatalytic degradation. This study develops a novel method to synthesize monoclinic phase lamellar BiVO 4 materials by simply changing the surfactant type. This study holds potential implications for advancing surfactant-assisted synthesis of high-efficiency photocatalysts.

Luminescent silver clusters that are confined inside porous zeolites have attracted great research interest due to the combined advantages of high quantum yield, tunable emission, excellent chemical stability, and desirable adoption ability of this micronano-composite. In this research, a series of Ag-exchanged R-LTA/Ag (R = Li, Na, K) zeolites were synthesized, in which the silver clusters showed blue-shifted excitation in the UV region, red-shifted emission in the visible region, and decreased emission intensity when taking Li + , Na + , and K + as the extra-framework cations, respectively. The [Ag 4 (H 2 O) x R 4 -sod] 6- ( x = 2, 4; R = Li, Na, K) structures were constructed, and the TD-DFT method was further carried out to study the influence of extra-framework cations on the luminescence performance of [Ag 4 ] 2+ clusters, in which the substitution of Al for Si and the reasonable hydrate levels were both taken into consideration. It is estimated that the S 1 and S 3 levels for the [Ag 4 (H 2 O) 4 Li 4 -sod] 6- cluster, the S 4 level for the [Ag 4 (H 2 O) 4 Na 4 -sod] 6- cluster, and the S 5 level for the [Ag 4 (H 2 O) 2 K 4 -sod] 6- cluster can be effectively populated through direct excitation, and the S 1 → S 0 transition is assumed to be responsible for the radiative emission in the visible region for the [Ag 4 ] 2+ pseudo-tetrahedrons. This calculated energy level diagram and simulated absorption spectra of [Ag 4 (H 2 O) x R 4 -sod] 6- ( x = 2, 4; R = Li, Na, K) clusters explained the modified luminescence property of silver clusters in R-LTA/Ag (R = Li, Na, K) zeolites studied in this research and reported literature.

Interface engineering strategies passivate defects on the polycrystalline perovskite film surface and improve the stability of corresponding perovskite solar cells (PSCs). However, a single interface engineering step can result in restricted benefits on various occasions. Therefore, an appropriate additional modification step can be necessary to synergistically improve the device performance. In this study, a two-step interface engineering strategy is developed. Initially, the CsPbI 3 perovskite surface is modified by choline iodide (ChI) to construct a 1D ChPbI 3 /3D CsPbI 3 heterojunction, and then an additional surface modification step with the use of crown ether is applied. The crown ether modification can further eliminate unpassivated surface defects after heterojunction construction. Benefiting from the inhibited interfacial recombination, the resultant carbon-electrode-based CsPbI 3 PSCs (C-PSCs) deliver a champion efficiency of 18.78%, representing one of the highest levels in this field. Besides, crown ether can synergistically improve the stability of the device against moisture, heat, and light stress due to the enhanced hydrophobicity and suppressed ion migration.

C-H···π interactions, a prevalent intermolecular force, play a pivotal role in chemistry, materials science, and life sciences. Despite extensive studies of their influence on intermolecular binding configurations and energetics, their impact on intermolecular coupling and charge transport remains unexplored. Here, we investigate the charge transport within supramolecular junctions connected by C-H···π and π-π interactions, respectively, and find that C-H···π interactions exhibit conductances that are 3.5 times those of π-π interactions. Angstrom-scale distance-dependent experiments indicate that the conductance of C-H···π supramolecular junctions experiences initial decay under stretching, followed by gradual convergence, in contrast with the periodic fluctuations in π-π stacked supramolecular junctions. Theoretical calculations show that charge transport within C-H···π interactions transitions from destructive to constructive quantum interference under stretching, with a larger range of constructive quantum interference compared with π-π stacking. This study establishes that C-H···π interactions facilitate efficient intermolecular charge transport and elucidates the evolution of quantum interference effects with assembly configuration, offering critical insights for the design of supramolecular materials and devices.

Automated segmentation and evaluation algorithms have been demonstrated to enhance the simplicity and translational utility of organoid technology. However, there is a pressing need for the development of complex organoids that possess epithelium environmental elements, dense regional cell aggregation, and intraorganoid morphologies. Nevertheless, there has been limited progress, including both the construction of data sets and the development of algorithms, in the use of user-friendly microscopy to address such complex organoids. In this study, a data set of bright-field and living cell fluorescence images in paired forms and with temporal variance was constructed using droplet-engineered lung organoids. Additionally, a large model-based algorithm was developed. Both the organoid contours and intraorganoid morphologies were included in the data set, and their physical parameters were included and screened to form multiplex digital markers for organoid evaluation. The algorithm has been demonstrated to outperform existing methods and is therefore suitable for the evaluation of complex organoids. It is expected that the algorithm will facilitate the successful demonstration of AI in organoid evaluation and decision-making regarding their status.

Tin (Sn)-based perovskite solar cells (TPSCs) have garnered significant attention recently, with power conversion efficiencies (PCEs) approaching 16%. Nevertheless, for Sn-based perovskites, their rapid crystallization and easy Sn 2+ oxidation are always annoying for fabricating efficient and stable TPSCs. Coordination engineering has been developed for retarding the crystallization rate and Sn 2+ passivation, but the homogeneous crystallization of Sn-based perovskites is still challenging due to the asymmetric and polar nature of currently used ligands. Here, a polarity-free S-containing symmetric molecule, 1,3,5-trithiane (TT), is developed to regulate the crystallization of FASnI 3 . Nonpolar TT with three symmetric S atoms shows equally strong coordination with Sn 2+ , which enhances the environment stability of the precursor and promotes the homogeneous nucleation and retarded growth of FASnI 3 crystals. Consequently, TT-based TPSCs exhibit an improved PCE from 9.02% to 12.87% with robust stability. This study highlights the critical role of ligand polarity in controlling the crystallization behavior of efficient TPSCs.

Psoriasis, an immune-mediated chronic inflammatory skin disease, is primarily diagnosed through clinical assessment. Currently, specific markers for the accurate diagnosis and prediction of psoriatic disease are lacking. Here, we employed a three-step designed study to perform untargeted metabolomics, with the aim of identifying candidate biomarkers for psoriasis. Through comprehensive multivariate and univariate statistical analyses, we screened eight potential biomarkers specific to psoriasis, with five structurally identified. Two dipeptide biomarkers, γ-GluSer and ThrGly, along with a lysine glycation metabolite, N α-fructosyl-lysine (Fruc-Lys), were found to be psoriasis biomarkers for the first time. Receiver operating characteristic curve analysis revealed that the area under the curve (AUC) values of these eight metabolites/features ranged from 0.68 to 0.94. A biomarker panel comprising ThrGly and feature m / z 120.0656 (C 4 H 9 NO 3 ) demonstrated high diagnostic accuracy (AUC = 0.97) in distinguishing psoriasis patients from healthy controls. Overall, our study identified and validated a panel of plasma metabolites/features that could serve as potential biomarkers for the diagnosis of psoriasis, providing new insights into the diagnosis and pathogenesis of this disease.

Extracellular vesicles (EVs) are emerging biomarkers in liquid biopsy that have gained increasing attention in disease diagnosis and prognosis monitoring. Most reported detection methods require the isolation of EVs from complex body liquids, often involving multiple washing steps to remove excess reagents and eliminate background interference. Nonetheless, these methods not only cause the loss of EVs but also result in poor repeatability and prolonged detection duration. The focus on wash-free detection methods is increasing due to the specific ability to avoid the removal of surplus reagents and, in some cases, even the isolation and purification of EVs. Viewing from different methodological perspectives, this review summarizes the recent advances in wash-free detection of EVs, containing aggregation induction, proximity sensing, allosteric probes, phase separation, Roman spectroscopy, field-effect transistor and microcantilever. The pros and cons of each detection strategy are impartially evaluated and this review concludes the prospects for future developments in this field.

The critical-sized bone defect resulting from trauma, tumor resection, and congenital deformity fails to undergo spontaneous healing due to its substantial size, while the ensuing inflammatory process and hypoxic environment further impede the regenerative process. Therefore, it has consistently presented a significant clinical challenge. In the present study, we incorporate a glycyrrhizic acid (GA)-functionalized hydrogel onto the surface of a Hydroxyapatite (Hap)-modified Polycaprolactone (PCL) scaffold to fabricate a composite scaffold. The composed scaffold showed favorable anti-inflammatory and antioxidative capabilities by modulating macrophage polarization and scavenging reactive oxygen species (ROS); the modification of Hap enhanced its osteogenic ability. An in vivo rat skull defect model confirmed that the composed scaffold efficiently promotes bone regeneration. In general, the composed scaffold with the ability of osteoimmune microenvironment regulation can effectively repair critical-sized bone defects. This strategy provides a promising method for the reconstruction of large segmental bone defects.

The Aurivillius phase layered perovskite ferroelectric material Sr 2 Bi 4 Ti 5 O 18 (SBTO) exhibits spontaneous polarization and piezoelectric properties, which confer significant potential for piezo-photocatalysis. Its ability to enhance electron-hole separation while providing excellent fatigue resistance positions it as a promising candidate in this field. Defects were introduced to improve the structural polarization and photoelectrochemical properties of SBTO. SBTO nanocrystals, featuring a mixed structure of hierarchically ordered mesoporous microflowers and nanosheets, were successfully synthesized via the hydrothermal method. The SBTO sample synthesized at a lower hydrothermal temperature displayed optimal oxygen vacancy concentration and exhibited superior piezoelectric-photo synergistic degradation activity for organic pollutants. Additionally, corona polarization increases the macroscopic polarization of the SBTO photocatalyst, promoting the separation of photogenerated carriers. Finite element simulations confirmed that a single flower-like SBTO structure generates a higher piezoelectric potential compared to a sheet-like morphology. In conclusion, integrating self-assembled hierarchical structure design, ferroelectric polarization, and defect engineering forms an effective strategy for achieving high-performance SBTO-based layered perovskite piezo-photocatalysts.

1,3-Difunctionalization of donor-acceptor cyclopropanes with copper nitrate and N -halosuccinimide was developed to efficiently afford γ-halonitrates. The pivotal factor of this protocol lies in the dual role of copper nitrate as a Lewis acid and an ideal nitrooxy source. The given approach features easy handling, good functional group compatibility, and wide substrate scope. Furthermore, various transformations of the obtained γ-chloronitrates underscore the remarkable synthetic potential inherent in this method.

MicroRNAs (miRNAs) in dermal interstitial fluid (ISF) have recently been recognized as clinically promising biomarkers for the diagnosis and prognosis of cancer. However, the detection poses significant challenges, primarily due to the low abundance of miRNAs and the limitations of current sampling techniques. To address this issue, we develop novel porous microneedles (PMNs) array-based sensor composed of poly(vinyl alcohol) porous hydrogel and DNA-templated silver nanoclusters (AgNCs) to facilitate the enrichment and highly sensitive detection of ISF miRNA. Leveraging the capillary action facilitated by its unique porous structure and the swelling properties of the hydrogel, the PMNs array can efficiently extract 2.7 ± 0.3 mg of ISF within 5 min. Additionally, the interconnected pores within the PMNs array contribute to an increased specific surface area, thereby offering a convenient platform for the decoration of DNA-templated AgNCs. The immobilized large amount of AgNCs effectively capture the target miRNA from the extracted ISF, resulting in miRNA-induced fluorescence quenching of AgNCs. Subsequently, the introduction of the duplex-specific nuclease leads to the cleavage of DNA in DNA-RNA heteroduplexes, which release miRNA to interact with other AgNCs. This process of target recycling triggers a further reduction in fluorescence intensity, thereby enabling sensitive detection of the low-abundant miRNA down to 1.6 pM. Both in vitro and in vivo experiments validate the efficacy of the AgNCs immobilized PMNs array for the detection of miRNA biomarkers in ISF within minutes. These results indicate that the proposed PMNs array-based sensor holds great potential for the development of noninvasive personalized diagnostic strategies.

Protein arginine methyltransferases (PRMTs) represent promising drug targets. However, the lack of isoform-selective chemical probes poses a significant hurdle in deciphering their biological roles. To address this issue, we devised a library of 100 diverse adenosine analogues, enabling a detailed exploration of the active site of PRMTs. Despite their close homology, our analysis unveiled specific chemical trends unique to the individual members. Notably, compound YD1130 demonstrated over 1000-fold selectivity for PRMT4 (IC 50 < 0.5 nM) over a panel of 38 methyltransferases, including the other PRMTs. Its prodrug YD1342 exhibited potent inhibition on cellular substrate methylation, breast cancer cell colony formation, and tumor growth in the animal model, surpassing or matching known PRMT4-specific inhibitors. In summary, our focused library not only illuminates the intricate active sites of PRMTs to facilitate the discovery of highly potent and isoform-selective probes but also offers a versatile blueprint for identifying chemical probes for other methyltransferases.

Nanolabels can enhance the detection performance of electrochemical biosensing methods, yet their practical application is hindered by complex preparation, batch-to-batch variability, and poor long-term storage stability. Herein, we present a novel electrochemical method for miRNA detection based on the just-in-time generation of zeolitic imidazolate framework-8 (ZIF-8) nanolabels initiated by nucleic acids. In this design, the target miRNA-21 is captured with magnetic beads and polyadenylated by Escherichia coli Poly(A) polymerase ( E PP), producing miRNA-21 molecules with poly(A) tails (miR-21-poly(A)). These molecules are then adsorbed onto a bare gold electrode (AuE) surface via adenine-gold affinity interactions, serving as nucleation sites for the rapid in situ formation of ZIF-8 nanoparticles. The ZIF-8 nanoparticles function as signal labels, impeding electron transfer at the electrode interfaces and thereby generating a notable electrochemical signal. The developed method demonstrated exceptional sensitivity, with a detection limit (LOD) as low as 2.3 aM and a linear detection range from 10 aM to 1000 fM. The practical application of the developed method was validated by using it to evaluate miRNA-21 expression levels in various biological samples, including cell lines, tumor tissues, and clinical blood samples from non-small cell lung cancer (NSCLC) patients. This approach simplifies the detection process by eliminating the need for presynthesized nanomaterials and premodified electrodes. Its simplicity and high sensitivity make this method a promising tool for point-of-care testing and a wide range of biomedical research applications.

Nonspecific reactive chemicals often interfere with the interpretation of high-throughput assay results because of their promiscuity and/or cytotoxicity. Using a high-throughput assay to identify such compounds is necessary to efficiently rule out potential assay artifacts. The MSTI, ( E )-2-(4-mercaptostyryl)-1,3,3-trimethyl-3 H -indol-1-ium, assay uses a thiol-containing fluorescent probe to screen for electrophile reactivity and could potentially be used to determine nonspecific reactive compounds. The Tox21 10K compound library was previously screened against a panel of ∼80 cell-based and biochemical assays, including the biochemical MSTI assay. In this study, we compared the MSTI assay activity of the Tox21 10K compounds with their promiscuity and cytotoxicity as reflected by their activities across the Tox21 assay panel to determine: (1) if this assay is predictive of a compound's promiscuity and cytotoxicity and (2) what chemical features create inconsistent results between the MSTI assay activity and promiscuity/cytotoxicity (false negatives and false positives). We found that the MSTI assay can predict a chemical's promiscuity/cytotoxicity with a 0.55 sensitivity and 0.97 specificity. Out of 3,407 unique compounds evaluated, we identified 92 false positive and 227 false negative results. Several structural features such as carboxamides and alkyl halides were found to be apparent in 53% ( p = 2.4 × 10 -07 ) and 19% ( p = 4.3 × 10 -06 ) of the false positives and negatives, respectively. The results of this analysis will help identify the potential challenges of this high-throughput assay and allow researchers to identify if a compound will be cytotoxic or promiscuous in an efficient manner.

A cell membrane-derived vesicle (MV) that has cell-mimicking features with characteristic functionalities holds vast appeal for biomimetic nanomedicine and drug delivery but suffers from a major limitation of innate fragility and poor stability. Herein, we report a lipid-anchoring strategy for stabilizing MV for enhanced drug delivery. An array of amphiphilic mono-acyl phosphatidylcholines (MPCs) with specific hydrophobic moieties are synthesized and readily engineered on MV based on their commendable aqueous solubility and efficient membrane insertability. Incorporation of MPCs containing rigid ring structures in the hydrophobic segment demonstrates the potency of stabilizing MV by the combined ordering and condensing effects. The optimized MPC-stabilized MV exhibits prolonged circulation in the bloodstream, elevated accumulation within a tumor, and enhanced therapeutic effects of chemotherapeutic and photothermal drugs. Moreover, doxorubicin-loaded MV, engineered with mono-all- trans retinoyl phosphatidylcholine as an MV stabilizer and a therapeutic prodrug, potently suppresses growth and metastasis of high-stemness tumors.

α-N-Methylation (Nα-methylation), catalyzed by protein N-terminal methyltransferases (NTMTs), constitutes a crucial post-translational modification involving the transfer of a methyl group from S -adenosyl-l-methionine (SAM) to the Nα-terminal amino group of substrate proteins. NTMT1/2 are known to methylate canonical Nα sequences, such as X-P-K/R. With over 300 potential human protein substrates, only a small fraction has been validated, and even less is known about the functions of Nα-methylation. This study delves into the characterizations of protein arginine deiminase 1 (PAD1) as a substrate of NTMT1. By employing biochemical and cellular assays, we demonstrated NTMT1-mediated Nα-methylation of PAD1, leading to an increase in protein half-life and the modulation of protein-protein interactions in HEK293T cells. The methylation of PAD1 appears nonessential to its enzymatic activity or cellular localization. Proteomic studies revealed differential protein interactions between unmethylated and Nα-methylated PAD1, suggesting a regulatory role for Nα-methylation in modulating PAD1's protein-protein interactions. These findings shed light on the intricate molecular mechanisms governing PAD1 function and expand our knowledge of Nα-methylation in regulating protein function.

Calcium is commonly the most abundant element in fire residues and its speciation largely determines the geochemical properties of fire residues and their effects on postfire soil chemistry. To explore the effects of biomass composition and fire conditions on ash Ca speciation, this study characterizes the speciation of Ca in charcoal and ash samples that were derived from different plant compartments and thermal conditions, using Ca K-edge X-ray absorption near edge spectroscopy. Results showed that biomass contains abundant organic Ca complexes, which were mineralized into fairchildite and calcite after heating at 450 to 600 °C and then CaO, as temperature increased to 750 °C. Apatite could be an abundant Ca species in fire residues if the Ca/P molar ratio of the biomass is small (<2). The mineralization of organic Ca to the identified Ca minerals during burning was negligibly affected by the oxygen level. Calcium speciation in prescribed fire residues resembled that of biomass ash burned at 550 °C with similar Ca/P molar ratios. Batch experiments showed that macronutrients (Ca, Mg, K, and P) were differentially released, as a result of different solubility of minerals in ashes and reprecipitation of minerals. The aqueous solubility of Ca, Mg, and P decreased as pH increased from 5 to 9, while K showed no pH dependency and was almost completely soluble. Results from this study improve our understanding of the chemistry of fire residues and their geochemical behaviors, which can help evaluate the impact of fire on postfire soil properties and macronutrient cycling.

The antibacterial mechanism of condensed tannins (CTs) obtained from tea has been elucidated, but the mechanism of legume-derived CTs remains unclear. The mechanisms of legume- and tea-derived CTs probably differ due to the diverse compositions of CTs. Previous research found that sainfoin CTs directly inhibited the growth of Pediococcus . The present study investigated the inhibition mechanism of CTs against Pediococcus pentosaceus SF11 (SF11) through proteomic analysis. The results showed that the minimum inhibitory concentration (MIC) of CTs against SF11 was 1500 mg/L and that CTs increased cell membrane permeability in a dose-dependent manner. In total, 418 differentially expressed proteins (DEPs) were identified between the CT treatment and the control, among which 341 were down-regulated and 77 were up-regulated in the CT treatment. The protein interaction network showed that the expression of only two DEPs was highly different between CT treated and control (|log2FC|> 2); the atp D protein was up-regulated in the CT-treated group, which was involved in ATP synthesis; down-regulated DEPs were most involved in lipoteichoic acid synthesis, peptidoglycan synthesis, and glycine metabolism. Twenty-seven proteins were not detected after CT treatment, which were involved in functions including fatty acid synthesis, RNA synthesis and translation, drug resistance, and cell membrane permeability in SF11. Therefore, the findings suggest that the inhibition mechanism of CTs may be related to cell membrane damage and inhibition of cell reproduction., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Given the extensive role of lipids in cancer development, there is substantial clinical interest in developing therapies that target lipid metabolism. In this study, we identified one cyclometalated iridium complex ( Ir2 ) that exhibits potent antiproliferation activity in MIA PaCa-2 cells by regulating fatty acid metabolism and sphingolipid metabolism simultaneously. Ir2 also efficiently overcomes cisplatin resistance in vitro . Satisfyingly, the generated Ir2@F127 carriers, as a temperature-sensitiv e in situ gelling system of Ir2 , showed effective cancer treatment with minimal side effects in an in vivo xenograft study. To the best of our knowledge, Ir2 is the first reported cyclometalated iridium complex that exerts anticancer activity in MIA PaCa-2 cells by intervening in lipid metabolism, which provides an alternative pathway for the anticancer mechanism of cyclometalated iridium complexes.

In the image Gaussian filtering process, convolving with a Gaussian matrix is essential due to the numerous arithmetic computations involved, predominantly multiplications and additions. This can heavily tax the system's memory, particularly with frequent use. To address this issue, a W/Ta 2 O 5 /Ag memristor was employed to substantially mitigate the computational overhead associated with convolution operations. Additionally, an interlayer of ZnO was subsequently introduced into the memristor. The resulting Ta 2 O 5 /ZnO heterostructure layer exhibited improved linearity in the pulse response, which enhanced linearity facilitates easy adjustment of the conductance magnitude through a linear mapping of the number of pulses and the conductance. Subsequently, the conductance of the W/Ta 2 O 5 /ZnO/Ag bilayer memristor was employed as the weights for the convolution kernel in convolution operations. Gaussian noise removal in image processing was achieved by assembling a 5 × 5 memristor array as the kernel. When denoising was performed using memristor arrays, compared to denoising achieved through Gaussian matrix convolution, an average loss of less than 5% was observed. The provided memristors demonstrate significant potential in convolutional computations, particularly for subsequent applications in convolutional neural networks (CNNs).

For solving the trade-off relationship of the polarization and breakdown electric field, ferroelectric films with high polarization are playing a critical role in energy storage capacitor applications, especially at moderate/low electric fields. In this work, we propose a multiscale structure (including defect, domain, and grain structures) synergetic optimization strategy to optimize the polarization behavior and energy storage performances of BiMg 0.5 Ti 0.5 O 3 (BMT) ferroelectric films by introducing Sr 0.7 La 0.2 TiO 3 (SLT) without compromising the breakdown strength. At a moderate electric field of 2917 kV/cm, a high discharge density of 72.2 J/cm 3 has been achieved in 0.9BMT-0.1SLT films, together with good frequency, thermal, and cycle stabilities for energy storage. Importantly, the phase difference Δφ is utilized to quantitatively evaluate the polarization switching mobility of the ferroelectric domain/PNRs at an external electric field stimulation. This research demonstrates that a multiscale structure optimization strategy could effectively regulate the energy storage performance, and ecofriendly BMT-based materials are promising candidates for next-generation energy storage capacitors, especially at moderate/low electric fields.

Superhydrophobic coatings have broad applications in a variety of industries. By using a low-surface-energy material and creating nanoscale roughness, a superhydrophobic surface can be produced. To overcome the health and environmental concerns of fluorine-based materials and the limitations of large-scale rough microstructure fabrication, a poly(dimethylsiloxane) (PDMS)-based hierarchical superhydrophobic fabric coating prepared by simple thermal treatment and electrostatic flocking technology was introduced in this study. High-temperature thermal treatment is employed to create PDMS nanoparticle-decorated carbon fibers, which are further vertically implanted onto the surface of cotton fabric via electrostatic flocking technology. The environmentally friendly PDMS nanoparticles were adopted as low-surface-energy materials, and the electrostatic flocking technology was utilized to generate a vertically aligned carbon fiber array coating, mimicking a lotus leaf-like superhydrophobic surface microstructure. Therefore, an ultrahigh water contact angle of 173.9 ± 2.8° and a low sliding angle of 1 ± 0.5° can be obtained by the fabric coating with a PDMS-to-carbon fiber ratio of 20:1. The prepared superhydrophobic fabric also exhibits an excellent self-cleaning property and great durability after 60 cycles of washing. Through commercially available thermal treatment and electrostatic flocking processes, this strategy for fabricating fluorine-free superhydrophobic fabric can be easily scaled up for commercial manufacturing and promotes the design of superhydrophobic coatings for other substrates.

Preparation of multifunctional metal-organic frameworks (MOFs) offers new opportunities to obtain ultrahigh synergistic catalytic performance for heterogeneous reactions; however, the application of a one-pot method for preparing multifunctional MOFs remains challenging. Herein, we develop a one-pot green route for synthesizing bimetallic nitro-functionalized UiO-66(Zr-Hf)-NO 2 with hierarchical porosity under solvent-free conditions. The optimal UiO-66(Zr-Hf 0.6 )-NO 2 shows an ultrahigh enhancement of oxidative desulfurization (ODS) efficiency to oxidize sulfur compounds (1000 ppm sulfur) in a model fuel at 40 °C within 12 min due to the introduction of more active Hf sites in the nodes, the increased Lewis acidity of Zr/Hf-O nodes by the electron-withdrawing NO 2 group, and the enhanced diffusion rates by the mesopores. The turnover frequency (TOF) over UiO-66(Zr-Hf 0.6 )-NO 2 at 40 or 50 °C reaches 145.3 or 217.0 h -1 that surpasses the TOF of most reported MOF-based catalysts in the ODS reaction. Quenching and electron paramagnetic resonance experiments confirm that the formed Hf-OH on the Zr/Hf-O nodes can easily decompose the oxidant (H 2 O 2 ) for generating a Hf-OOH-active intermediate and dominate the ODS efficiency. This contribution provides a one-pot solvent-free avenue to synthesize multifunctional MOFs for enhancing their catalytic activities for targeted applications.

We developed a protocol for the synthesis of highly functionalized 5,6-dihydro-imidazo[1,2- c ][1,2,3]triazole derivatives 4 - 5 (DHITs) from 1-diazonaphthalen-2(1 H )-one derivatives with heterocyclic ketene aminals (HKAs). This strategy involved cycloaddition and skeletal rearrangement entailing the heating of a mixture of substrates 1 with HKAs 2 - 3 and THF without any catalyst. As a result, a series of DHITs 4 - 5 were produced by cleaving one bond (1 C═N bond) and forming three bonds (1 N-N and 2 C-N bonds) in a single step. This protocol achieved the dual functionalization of diazo building blocks involving both the aromatic nitrogen alkylation reaction to form an ArC-N bond without any metal catalyst and the intermolecular cycloaddition of the N═N bond. These strategies can be used to synthesize functionalized DHITs for combinatorial and parallel syntheses via one-pot reactions without any catalyst.

Platelet-derived extracellular vesicles (PEVs) showing great potential in wound healing have attracted increasing attention recently. Nondestructive isolation and effective utilization strategies are highly conducive for PEVs developing into recognized therapeutic entities. Here, we present an efficient strategy for PEV isolation and bacterial infected wound healing based on self-assembled DNA microflowers. First, DNA microflowers are prepared using rolling circle amplification. Then, the hydrophobic interaction between cholesteryl modified on DNA microflowers and the phospholipid bilayer membrane of PEVs leads to the formation of a network structure with improved mechanical strength and the separation of PEVs from biological samples. Finally, controlled release of PEVs is achieved through bacterial-induced hydrogel degradation. In vitro experiments demonstrate the obtained DNA hydrogel with good cytocompatibility and therapeutic potential. Taken together, the DNA microflower-based hydrogels with bioadhesive, self-healing, tunable mechanical properties and bacteria-responsive behavior offer substantial potential for EV isolation and wound healing.

In this study, in the presence of a certain amount of cuprous chloride catalyst and the synergistic action of ligand and base, the P-H bond activation of secondary biarylphosphine oxides and the attack on the β-site of orthoaryl groups were investigated. Phosphafluorene oxide was synthesized by C-H bond activation and an intramolecular dehydrogenation coupling reaction to construct a C-P bond. Subsequently, we conducted a control experiment and made reasonable speculations about its mechanism. In addition, the use of phosphafluorene as a ligand in some synthetic catalytic reactions has shown excellent results, demonstrating its excellent catalytic properties.

Insufficient antigen self-presentation of tumor cells and ineffective antigen cross-presentation by dendritic cells (DCs) contribute to diminished immune recognition and activation, which cause resistance to immunotherapies. Herein, we present an ultrasound-activatable in situ vaccine by utilizing a hybrid nanovesicle composed of a thylakoid (TK)/platelet (PLT) membrane and a liposome encapsulating DNA methyltransferase inhibitor zebularine (Zeb) and sonosensitizer hematoporphyrin monomethyl ether (HMME). Upon local exposure to ultrasound, reactive oxygen species (ROS) are generated and induce the sequential release of the payloads. Zeb can efficiently inhibit tumor DNA hypermethylation, promoting major histocompatibility complex class I (MHC-I) molecules-mediated antigen self-presentation to improve immune recognition. Meanwhile, the catalase on the TK membrane can decompose the tumoral overexpressed H 2 O 2 into O 2 , which boosts the generation of ROS and the destruction of tumor cells, resulting in the in situ antigen release and cross-presentation of tumor antigens by DCs. This in situ vaccine simultaneously promotes antigen self-presentation and cross-presentation, resulting in heightened antitumor immunity to overcome resistance.

The self-renewal and differentiation properties of cancer stem cells (CSCs) result in chemoresistance in breast cancer. Even though numerous drugs have been developed to target CSCs, they have suffered from inefficient delivery and accumulation at the focal site. Here, a thermoresponsive hydrogel is developed by coencapsulating aggregation-induced emission (AIE)-active photothermal agent and thioridazine (THZ), demonstrating a controllable delivery system triggered by the AIE agent to augment THZ-mediated CSC ablation. Upon near-infrared laser stimuli, the photothermal effect from the AIE agent induces hydrogel deformation for burst drug release. The precise in situ tumor administration of the hydrogel accelerates drug diffusion and accumulation in deep breast cancer lesions. Thus, THZ can invade tumors and provoke massive CSC apoptosis via dopamine receptor blockage and oxidative stress induction. Consequently, effective CSC inhibition and significant suppression of tumor recurrence and metastasis are demonstrated in mice with breast cancer. We believe that this intelligent hydrogel-based delivery system represents a promising treatment strategy for metastatic breast cancer with clinical potential.

Triple-negative breast cancer (TNBC) is characterized by high malignancy and limited treatment options. Given the pressing need for more effective treatments for TNBC, this study aimed to develop platelet membrane (PM)-camouflaged silver metal-organic framework nanoparticles (PM@MOF-Ag NPs), a biomimetic nanodrug. PM@MOF-Ag NP construction involved the utilization of 2-methylimidazole and silver nitrate to prepare silver metal-organic framework (MOF-Ag) NPs. The PM@MOF-Ag NPs, due to their camouflage, possess excellent blood compatibility, immune escape ability, and a strong affinity for 4T1 tumor cells. This enhances their circulation time in vivo and promotes the aggregation of PM@MOF-Ag NPs at the 4T1 tumor site. Importantly, PM@MOF-Ag NPs demonstrated promising antitumor activity in vitro and in vivo. We further revealed that PM@MOF-Ag NPs induced tumor cell death by overproducing reactive oxygen species and promoting cell apoptosis. Moreover, PM@MOF-Ag NPs enhanced apoptosis by upregulating the ratios of Bax/Bcl-2 and cleaved caspase3/pro-caspase3. Notably, PM@MOF-Ag NPs exhibited no significant organ toxicity, whereas the administration of MOF-Ag NPs resulted in liver inflammation compared to the control group.

Triple-negative breast cancer (TNBC) represents a highly aggressive and heterogeneous malignancy. Currently, effective therapies for TNBC are very limited and remain a significant unmet clinical need. Targeting the transcription-regulating cyclin-dependent kinase 9 (CDK9) has emerged as a promising avenue for therapeutic treatment of TNBC. Herein, we report the design, synthesis, optimization, and evaluation of a new series of aminopyrazolotriazine compounds as orally bioavailable, potent, and CDK9/2 selectivity-improved inhibitors, enabling efficacious inhibition of TNBC cell growth, as well as notable antitumor effect in TNBC models. The compound C35 demonstrated low-nanomolar potency with substantially improved CDK9/2 selectivity, downregulated the CDK9-downstream targets ( e.g. , MCL-1), and induced apoptosis in TNBC cell lines. Moreover, with the desired oral bioavailability, oral administration of C35 could significantly suppress the tumor progression in two TNBC mouse models. This study demonstrates that target transcriptional regulation is an effective strategy and holds promising potential as a targeted therapy for the treatment of TNBC.

Macrophages play a pivotal role in the crosstalk between the immune and skeletal systems, while Mg-based biomaterials demonstrate immunomodulatory capabilities in this procedure. However, the mechanism of how Mg 2+ promotes osteogenesis through the interplay of bone marrow-derived mesenchymal stem cells (BMSCs) and macrophages remains undescribed. Here, we demonstrated that a Mg-cross-linked alginate hydrogel exerted a dual enhancement of BMSCs osteogenic differentiation through the ligand-receptor pairing of the OSM/miR-370-3p-gp130 axis. On the one hand, Mg 2+ , released from the Mg-cross-linked hydrogel, stimulates bone marrow-derived macrophages to produce and secrete more OSM. On the other hand, Mg 2+ lowers the miR-370-3p level in BMSCs and in turn, reverses its suppression on gp130. Then, the OSM binds to the gp130 heterodimer receptor and activates intracellular osteogenic programs in BMSCs. Taken together, this study reveals a novel cross-talk pattern between the skeletal and immune systems under Mg 2+ stimulation. This study not only brings new insights into the immunomodulatory properties of Mg-based biomaterials for orthopedic applications but also enriches the miRNA regulatory network and provides a promising target to facilitate bone regeneration in large bone defects.

Curcumin has demonstrated promising preclinical antiobesity effects, but its low bioavailability makes it difficult to exert its full effect at a suitable dose. The objective of this study was to screen curcumin derivatives with enhanced bioavailability and lipid-lowering activity under the guidance of computer-aided drug design (CADD). CAAD was used to perform virtual assays on curcumin derivatives to assess their pharmacokinetic properties and effects on pancreatic lipase activity. Subsequently, 19 curcumin derivatives containing 5 skeletons were synthesized to confirm the above virtual assay. The in vitro pancreatic lipase inhibition assay was employed to determine the half-maximal inhibitory concentration (IC 50 ) of these 19 curcumin derivatives. Based on CADD analysis and in vitro pancreatic lipase inhibition, 2 curcumin derivatives outperformed curcumin in both aspects. Microscale thermophoresis (MST) experiments were employed to assess the binding equilibrium constants ( K d ) of the aforementioned 2 curcumin derivatives, curcumin, and the positive control drug with pancreatic lipase. Through virtual screening utilizing a chemoinformatics database and molecular docking, 6 derivatives of curcumin demonstrated superior solubility, absorption, and pancreatic lipase inhibitory activity compared to curcumin. The IC 50 value for 1,7-bis(4-hydroxyphenyl)heptane-3,5-dione (C4), which displayed the most effective inhibitory effect, was 42.83 μM, while the IC 50 value for 1,7-bis(4-hydroxy-3-methoxyphenyl)heptane-3,5-dione (C6) was 98.62 μM. On the other hand, the IC 50 value for curcumin was 142.24 μM. The MST experiment results indicated that the K d values of C4, C6, and curcumin were 2.91, 18.20, and 23.53 μM, respectively. The results of the activity assays exhibited a relatively high degree of concordance with the outcomes yielded by CADD screening. Under the guidance of CADD, the targeted screening of curcumin derivatives with excellent properties in this study exhibited high-efficiency and low-cost benefits., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The exceptional biocompatibility and adaptability of hydrogels have garnered significant interest in the biomedical field for the fabrication of biomedical devices. However, conventional synthetic hydrogels still exhibit relatively weak and fragile properties. Drawing inspiration from the photosynthesis process, we developed a facile approach to achieve a harmonious combination of superior mechanical properties and efficient preparation of silk fibroin hydrogel through photo-cross-linking technology, accomplished within 60 s. The utilization of riboflavin and H 2 O 2 enabled a sustainable cyclic photo-cross-linking reaction, facilitating the transformation from tyrosine to dityrosine and ultimately contributing to the formation of highly cross-linked hydrogels. These photo-cross-linking hydrogels exhibited excellent elasticity and restorability even after undergoing 1000 cycles of compression. Importantly, our findings presented that hydrogel-encapsulated adipose stem cells possess the ability to stimulate cell proliferation along with stem cell stemness. This was evidenced by the continuous high expression levels of OCT4 and SOX2 over 21 days. Additionally, the utilization of photo-cross-linking hydrogels can be extended to various material molding platforms, including microneedles, microcarriers, and bone screws. Consequently, this study offered a significant approach to fabricating biomedical hydrogels capable of facilitating real-time cell delivery, thereby introducing an innovative avenue for designing silk devices with exceptional machinability and adaptability in biomedical applications.

Surface-initiated iron(0)-mediated controlled radical polymerization (SI-Fe 0 CRP) with low toxicity and excellent biocompatibility is promising for the fabrication of biofunctional polymer coatings. However, the development of Fe(0)-based catalysts remains limited by the lower dissociation activity of the Fe(0) surface in comparison to Cu(0). Here, we found that, by simply polishing the Fe(0) plate surface with sandpaper, the poly(methacryloyloxy)ethyl trimethylammonium chloride brush growth rate has been increased significantly to 3.3 from 0.14 nm min -1 of the pristine Fe(0) plate. The excellent controllability of roughness-mediated SI-Fe 0 CRP can be demonstrated by customizing multicompartment brushes and triblock brushes. Furthermore, we found that the resulting polymer brush coatings exhibit remarkably low water adhesion (0.097 mN) and an outstanding drag reduction rate of 52% in water. This work provides a promising strategy for regulating the grafting rate of polymer brushes via SI-Fe 0 CRP for biocompatible marine drag reduction coatings.

We present a reduced-cost implementation of the state-averaged driven similarity renormalization group (SA-DSRG) based on the frozen natural orbital (FNO) approach. The natural orbitals (NOs) are obtained by diagonalizing the one-body reduced density matrix from SA-DSRG second-order perturbation theory (SA-DSRG-PT2). We consider three criteria to truncate the virtual NOs for the subsequent electron correlation treatment beyond SA-DSRG-PT2. An additive second-order correction is applied to the SA-DSRG Hamiltonian to reintroduce correlation effects from the discarded orbitals. The FNO SA-DSRG method is benchmarked on 35 small organic molecules in the QUEST database. When keeping 98-99% of the cumulative occupation numbers, the mean absolute error in the vertical transition energies due to FNO is less than 0.01 eV. Using the same FNO threshold, we observe a speedup of 9 times compared to the conventional SA-DSRG implementation for nickel carbonyl with a quadruple-ζ basis set. The FNO approach enables nonperturbative SA-DSRG computations on chloroiron corrole [FeCl(C 19 H 11 N 4 )] with more than 1000 basis functions, surpassing the current limit of a conventional implementation.

Promising targeted therapy options to overcome drug resistance and side effects caused by platinum(II) drugs for treatment in hepatocellular carcinoma are urgently needed. Herein, six novel multifunctional platinum(IV) complexes through linking platinum(II) agents and glycyrrhetinic acid (GA) were designed and synthesized. Among them, complex 20 showed superior antitumor activity against tested cancer cells including cisplatin resistance cells than cisplatin and simultaneously displayed good liver-targeting ability. Moreover, complex 20 can significantly cause DNA damage and mitochondrial dysfunction, promote reactive oxygen species generation, activate endoplasmic reticulum stress, and eventually induce apoptosis. Additionally, complex 20 can effectively inhibit cell migration and invasion and trigger autophagy and ferroptosis in HepG-2 cells. More importantly, complex 20 demonstrated stronger tumor inhibition ability than cisplatin or the combo of cisplatin/GA with almost no systemic toxicity in HepG-2 or A549 xenograft models. Collectively, complex 20 could be developed as a potential anti-HCC agent for cancer treatment.

Water dissociation remarkably affects the CO 2 reduction to CO and HCOOH, but whether it is effective for two-carbon product formation on M-N x -containing catalysts is still ambiguous. Herein, by using a fluorinated metal phthalocyanine (MPc-F) as the M-N 4 -based model electrocatalyst, experimental and theoretical results reveal that the H 2 O-dissociation-induced active H species decrease the overpotential of the *CO hydrogenation to *CHO and facilitate the C-C coupling between *CHO and neighboring CO. Such an effect is strengthened by an increase in the *CO binding strength on the metal center. By introducing CuPc as the H 2 O dissociation catalyst into MPc-F (MPc-F/CuPc) to accurately regulate the H 2 O dissociation, the faradic efficiency of C2 products on FePc-F/CuPc and MnPc-F/CuPc increases from 0% (FePc-F and MnPc-F) to 26 and 36%, respectively. This work develops a novel strategy for enhancing the selectivity of M-N x -containing catalysts to C2 products and reveals the correlation between H 2 O dissociation and C2 product formation.

The stability of both the structure and activity of MoS 2 nanocatalysts is crucial for minimizing the catalyst cost of the slurry-phase (SP) catalytic hydrogenation. MoS 2 -GP and MoS 2 -SP catalysts were, respectively, obtained by gas-phase (denoted as GP) and SP aging of fresh MoS 2 catalysts. The MoS 2 -SP catalyst demonstrated a comparable catalytic hydrogenation activity to that of the fresh MoS 2 catalyst, which is about 1.7 times of that for the MoS 2 -GP catalyst. After 12 cycles of the MoS 2 -SP catalyst, the obtained Cy12 catalyst demonstrates a retention of 92.0% of its initial catalytic activity. The MoS 2 -SP catalyst exhibits an impressive stability of catalytic hydrogenation. The MoS 2 -SP catalyst exhibits average stacking layers of 3.3 and an average slab of 5.2 nm and exposes 14.0% of active sites. The MoS 2 -SP catalyst can serve as a highly active and stable catalyst for catalytic hydrogenation. This finding can offer valuable insights into the stability of the hydrogenation catalyst in SP hydrogenation technology., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The structure of solvated Li + has a significant influence on the electrolyte/electrode interphase (EEI) components and desolvation energy barrier, which are two key factors in determining the Li + diffusion kinetics in lithium metal batteries. Herein, the "solvent activity" concept is proposed to quantitatively describe the correlation between the electrolyte elements and the structure of solvated Li + . Through fitting the correlation of the electrode potential and solvent concentration, we suggest a "low-activity-solvent" electrolyte (LASE) system for deriving a stable inorganic-rich EEI. Nano LiF particles, as a model, were used to capture free solvent molecules for the formation of a LASE system. This advanced LASE not only exhibits outstanding antidendrite growth behavior but also delivers an impressive performance in Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 cells (a capacity of 169 mAh g -1 after 250 cycles at 0.5 C).

Chronic wound repair is a clinical treatment challenge. The development of multifunctional hydrogels is of great significance in the key aspects of treating chronic wounds, including reducing oxidative stress, promoting angiogenesis, and improving the natural remodeling of extracellular matrix and immune regulation. In this study, we prepared a composite hydrogel, sodium alginate (SA)@MnO 2 /recombinant humanized collagen III (RHC)/mesenchymal stem cells (MSCs), composed of SA, MnO 2 nanoparticles, RHC, and MSCs. The hydrogel has high mechanical properties and good biocompatibility. In vitro, SA@MnO 2 /RHC/MSCs hydrogel effectively enhanced the formation of intricate tubular structures and angiogenesis and showed synergistic effects on cell proliferation and migration. In vivo, the SA@MnO 2 /RHC/MSCs hydrogel enhanced diabetes wound healing, rapid re-epithelization, favorable collagen deposition, and abundant wound angiogenesis. These findings demonstrated that the combined effects of SA, MnO 2 , RHC, and MSCs synergistically accelerate healing, resulting in a reduced healing time. These observed healing effects demonstrated the potential of this multifunctional hydrogel to transform chronic wound care and improve patient outcomes.

Gas-liquid interfaces have a unique structure different from the bulk phase due to the complex intermolecular interactions within them and are regarded as barriers that prevent gases from entering solution or as channels that affect gas reactions. In this study, the adsorption and mass-transfer mechanisms of sulfur dioxide and nitric oxide at the gas-liquid interface of a H 2 O 2 solution were comprehensively analyzed using molecular dynamics (MD) simulations. The analysis on molecule angle showed that H 2 O molecules tended to align parallel to the solution surface on the surface of the H 2 O 2 solution. Regardless of whether the gas was adsorbed on the surface of the solution or not, H 2 O 2 molecules were always perpendicular to the interface of the solution. The analysis on molecule angle and radial distribution function revealed that the H atoms of H 2 O molecules had a corresponding turn, and SO 2 molecules were greatly affected by the attraction of H 2 O 2 molecules during the adsorption of gas molecules on the interface. Steered MD was utilized to investigate the mass-transfer process of SO 2 and NO molecules across the gas-liquid interface. The S atoms of SO 2 molecules were significantly influenced by H 2 O 2 molecules, while the O atoms of NO molecules gradually transitioned from the gas phase to the liquid phase. The results provided information on how gas molecules interacted with the surface of the solution and the specific details of the molecular orientation at the solution surface.

Herein, a novel and practical methodology for the photoinduced decarboxylative difluoroalkylation and perfluoroalkylation of α-fluoroacrylic acids is reported. A wide range of α-fluoroacrylic acids can be used as applicable feedstocks, allowing for rapid access to structurally important difluoroalkylated and polyfluoroalkylated monofluoroalkenes with high Z-stereoselectivity under mild conditions. The protocol demonstrates excellent functional group compatibility and provides a platform for modifying complex biologically active molecules.

Developing advanced electrolytes has been regarded as a pivotal strategy for enhancing the electrochemical performance of batteries; however, the criteria for electrolyte design remain elusive. In this study, we present an electrolyte design chart reframed through intermolecular interactions. By combining systematic nuclear magnetic resonance, Fourier transform infrared measurements, molecular dynamics (MD) simulations, and machine-learning-assisted classifications, we establish semiquantitative correlations between electrolyte components and the electrochemical reversibility of electrolytes. We propose the equivalent increment of Li salt resulting from functional cosolvent and solvent-solvent interactions for effective electrolyte design and prediction. The controllable regulation of the electrolyte design chart by the properties of solvent-solvent interactions presents varying equivalent effects of increasing Li salt concentrations in different electrolyte systems. Based on this mechanism, we demonstrate highly reversible and nonflammable phosphate-based electrolytes for graphite||NCM811 full cells. The proposed electrolyte design chart, semiquantitatively determined by intermolecular interactions, provides the necessary experimental foundation and basis for the future rapid screening and prediction of electrolytes using machine-learning methods., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The development of high-performance biosensors is a key focus in the nanozyme field, but the current limitations in biocompatibility and recyclability hinder their broader applications. Herein, we address these challenges by constructing core-shell nanohybrids with biocompatible poly(ethylene glycol) (PEG) modification using a galvanic replacement reaction between orthovanadate ions and liquid metal (LM) (VO x @EGaIn-PEG). By leveraging the excellent charge transfer properties and the low band gap of the LM surface oxide, the VO x @EGaIn-PEG heterojunction can effectively convert hydrogen peroxide into hydroxyl radicals, demonstrating excellent peroxidase-like activity and stability ( K m = 490 μM, v max = 1.206 μM/s). The unique self-healing characteristics of LM further enable the recovery and regeneration of VO x @EGaIn-PEG nanozymes, thereby significantly reducing the cost of biological detection. Building upon this, we developed a nanozyme colorimetric sensor suitable for biological systems and integrated it with a smartphone to create an efficient quantitative detection platform. This platform allows for the convenient and sensitive detection of glucose in serum samples, exhibiting a good linear relationship in the range of 10-500 μM and a detection limit of 2.35 μM. The remarkable catalytic potential of LM, combined with its biocompatibility and regenerative properties, offers valuable insights for applications in catalysis and biomedical fields.