Accurate quantification of edible-oil adulteration is constrained by an open-world problem: adulterants encountered at deployment often differ from those seen during training. Here we show that olive-oil volume fraction can be reliably recovered from excitation-emission matrix (EEM) fluorescence spectra even when the adulterant is entirely unseen during training. We propose an optimal-transport (OT) framework that aligns source- and target-domain spectral distributions in an unsupervised manner, requiring no target-domain concentration labels. Under a stringent leave-one-adulterant-out protocol across five adulterant systems, the OT-aligned support vector regression model achieves a mean R2 of 0.965 (s.d. = 0.004), substantially outperforming raw spectra (R2 = 0.831), PCA (R2 = 0.693) and PARAFAC (R2 = 0.659). These results indicate that olive-oil concentration is encoded as an intrinsic geometric coordinate within the spectral distribution, recoverable by optimal transport without adulterant-specific supervision.

Traditional inorganic semiconductor gas sensors operate at elevated temperatures and exhibit inherent rigidity and brittleness, thereby limiting their application in wearable electronics. Herein, organic-inorganic YSZ@PANI/SnS2 heterojunction composite nanofiber film are fabricated through a sequential process involving electrospinning, oxidative polymerization, and hydrothermal treatment. Benefited from the employment of PANI interfacial layer, biomimetic "branch-leaf" structure featuring vertically grown, network-like SnS2 nanosheets, the stress and energy are dispersed and dissipate effectively, therefore enhance the mechanical flexibility. Simultaneously, the vertically staggered SnS2 nanosheets accelerating the gas diffusion/transmission and providing abundant active sites. The formation of PANI/SnS2 heterojunction, which endows the composite with elevated conductivity, reaction activity, and carrier transport separation efficiency. At room temperature (RT, 25 degrees C), the device exhibits high response value and response/recovery times of 9.35 and 12/25 s to 2 ppm NO2, respectively. Furthermore, the device maintains satisfactory responsiveness even under bending conditions. This research presents a promising novel approach for fabricating organic-inorganic composite nanofibers, which may contributes to the development of flexible RT gas sensors.

Vibrio parahaemolyticus is a notorious seafood-borne pathogen associated acute gastroenteritis, posing increasing challenge to global food security and public health. Bile represents one of the most important factors that affect its intestinal colonization. And bacteria usually employ shared strategies to resist bile salts alongside other environmental stresses. To identify the essential genes for stresses adaptation in V. parahaemolyticus, we screened a genome-wide transposon-insertion library for bile hypersensitive mutants and identified vpa1463, encoding a conserved but uncharacterized DUF1566-domain protein, as essential for bile tolerance. The deletion of vpa1463 drastically reduced the bile salts minimum inhibitory concentration MIC from 2.5% (wild-type) to 0.3% (Δvpa1463), and inhibited swarming and swimming motilities. Mechanistic analyses revealed that the deletion of vpa1463 increases outer-membrane (OM) permeability, compromises its integrity, and decreases efflux activity. Data-independent acquisition (DIA)-based proteomics identified 1156 differentially expressed proteins in the vpa1463 mutant compared to the wild type, including key proteins associated with efflux pumps and porins, as well as those involved in flagellar biosynthesis. Moreover, the mutation of vpa1463 led to attenuated biofilm formation and decrease its colonization on food processing contact materials or food surfaces by approximately one order of magnitude. These membrane defects led to a cascade of phenotypic failures in Δvpa1463, impaired motility, heightened susceptibility to antibiotics, food-grade disinfectants and organic acids. Collectively, Our data demonstrate that Vpa1463 is a vital contributor to membrane homeostasis and environmental fitness, making it a promising target for strategies to mitigate V. parahaemolyticus contamination in the food industry and prevent human infection.

The anthrax protective antigen self-assembles into a heptameric transmembrane channel under acidic conditions, exhibiting characteristic biological nanopore properties. However, the anthrax channel faces significant challenges in single-molecule nanopore sensing due to inherent instability issues such as sudden current attenuation, frequent channel occlusion and noise interference, primarily mediated by phenylalanine clamps within the channel lumen. To address these limitations on nanopore sensing, we designed four electrolyte systems (KCl, NaCl, LiCl, and 1-butyl-3-methylimidazolium chloride [BMIM]Cl) with asymmetric ionic strength and pH condition to stabilize the anthrax nanopore platform. While traditional alkali metal chlorides (KCl, NaCl, LiCl) showed partial improvement in electrical properties, the [BMIM]Cl system with pH asymmetry enabled a stable nanopore with optimal electrical characteristics, including diminished channel occlusion, enhanced signal-to-noise ratio, steady discrete constant and current strength of open-pore, all indicative of uniform ion transport. Furthermore, the stabilized anthrax nanopore demonstrated exceptional molecular detection capability, resolving single-molecule discrimination of homologous peptides of MAPKK gene families which are key signaling proteins involved in the regulation of various biology processes in eukaryotic organisms. This work establishes a robust nanopore platform for high-resolution small-molecule detection and highlights the unique advantages of ionic liquids in regulating nanoscale molecule transport.

A unique coherent bremsstrahlung (CB) regime is proposed for the generation of an isolated half-cycle attosecond pulse (AP), even for the case of a multicycle driving laser pulse, which is realized by the laser pulse interacting with the double-foil target. When the rising edge of the laser pulse interacts with the double-foil target, the AP train is generated in the reflected direction due to the fact that the relativistic electron sheet (RES) is generated periodically twice per cycle of the laser pulse. While the peak cycle of the laser pulse interacts with the target, the electrons of the second foil target were nearly completely removed, which leads to the formation of an electrostatic potential well, and then the double-foil target becomes an electrostatic storage target (EST) that can capture and store electrons coming from the second foil target. Accordingly, only one RES can be generated by the peak cycle of the laser pulse interacting with those electrons stored in the EST, and is accelerated to ultra-relativistic velocity in the transmission direction, which emits the isolated AP by the CB regime. The isolation regime of AP can be determined by the scaling law of the depletion of electrons, which is described by the ratio of the areal charge density of the double-foil target and the amplitude of the peak-cycle laser pulse. The ratio is called the generalized similarity parameter. The generalized similarity parameter is about 2/π, which is predicted by the theoretical model and confirmed by the simulation results. The robustness of the isolation regime of AP is confirmed by considering different parameters of the laser pulse and plasmas, and by considering the presence of preplasma and two-dimensional effects.

The influence of quantum mechanics on the dynamics of chemical reactions is unknown for many processes in chemistry. Chemical reaction dynamics are often well described by quasiclassical motion of the atoms on quantum mechanical Born-Oppenheimer potential energy surfaces. Here we present a dynamic isotope effect in a nucleophilic substitution reaction experiment that can only be explained by quasiclassical trajectory simulations for reactants containing deuterium atoms, but not when hydrogen atoms are involved. The calculated energy- and angle-differential cross sections are compared to experimental crossed-beam velocity map imaging data, which show significantly more forward scattering for hydrogenated compared to deuterated reactants. Quantum scattering calculations in reduced dimensions explain this by an increased reaction probability for large total angular momentum, a feature that is not captured in the quasiclassical approach.

Vibrio parahaemolyticus (V. parahaemolyticus), a Gram-negative halophilic bacterium, is a leading seafood-borne pathogen that can cause acute gastroenteritis. Outer membrane (OM) porins are involved in exporting extracellular polymeric substances, which is essential for biofilm formation. However, the contribution of porins to the biofilm formation of V. parahaemolyticus is still obscure. We recently found that a mutation in the DHH/DHHA1 family gene vp2835 enhances biofilm formation in V. parahaemolyticus but inhibits its motility. Here, we identified an OM porin gene, vpa0810, from Δvp2835 strain. The deletion of vpa0810 in the wild type strain resulted in the inhibition of both swarming and swimming motility, while reverted the motility defect of Δvp2835. The Δvpa0810 decreased its biofilm formation capability in both the wild type and the Δvp2835 strain. Additionally, the surface hydrophobicity, auto-aggregation, OM permeability, and exopolysaccharides (EPS) content were decreased in the Δvpa0810 strain. Interestingly, qRT-PCR results demonstrated that the genes involved in EPS synthesis (cpsA, scvE, and cpsF) and the porin gene ompW were significantly up-regulated in the Δvpa0810 strain, but down-regulated in the Δvp2835-Δvpa0810 double mutant. Furthermore, the deletion of vpa0810 compromised its ability to form biofilm on silicon wafers, glass, stainless-steel plates, as well as on shrimp and crab surfaces. The vpa0810 deletion mutation also reduced its stress tolerance to bile salt, low pH, low temperature, and the antibiotics colistin. In summary, our data suggest that Vpa0810 may regulate biofilm formation through EPS biosynthesis and exportation, which might provide a new target for developing control strategies against V. parahaemolyticus.

Objectives This study aims to explore whether isoimperatorin (ISOIM) regulates the malignant phenotype of T‑cell acute lymphoblastic leukemia (T-ALL) cells through the PI3K/AKT pathway and programmed cell death ligand-1 (PD-L1). Methods Through in vitro experiments, ISOIM on T-ALL cell proliferation and apoptosis was evaluated using the cell counting kit-8 and EdU assays, flow cytometry, and TUNEL staining. Network pharmacology, molecular docking, and functional enrichment analyses were conducted to analyze the underlying mechanisms of ISOIM. Changes in apoptosis-related proteins, PD-L1 protein, and PI3K/AKT pathway-related proteins were assessed by western blotting. Results ISOIM inhibited T-ALL cell proliferation, promoted apoptosis, decreased Bcl-2 levels, and increased C-caspase-3 and Bax levels. KEGG and GO enrichment analyses indicated that the overlapping targets between ISOIM and ALL were related to the PD-1 checkpoint and PI3K/AKT pathway. Molecular docking analysis showed good binding between ISOIM and PIK3CA (also known as PI3K). ISOIM reduced PD-L1, p-PI3K, p-AKT, and p-mTOR levels. Moreover, the PI3K/AKT pathway activator 740 Y-P reversed the inhibitory effect of ISOIM on PD-L1 expression and the malignant behavior of T-ALL cells. Conclusions ISOIM inhibited the malignant behavior of T-ALL cells and reduced PD-L1 levels by suppressing the PI3K/AKT pathway. This study provides a theoretical basis for developing novel treatment strategies for ALL.

Bimolecular nucleophilic substitution (SN2) reactions in the gas phase are of great importance in chemistry, whose microscopic mechanisms are, however, not comprehensively understood. In this work, the mode-specific quantum dynamics of the prototypical SN2 reaction F- + CH3I → I- + CH3F are investigated using reduced six-dimensional quantum wave packet and full-dimensional quasi-classical trajectory methods. The reaction probabilities are calculated for both the ground and excited vibrational states of the reactant CH3I at collision energies up to 2.3 eV. The results show that the CH stretching vibration slightly suppresses the reaction with collision energies below 0.4 eV, becomes a spectator mode in the collision energy range of 0.4-1.5 eV, and then enhances the reaction at higher collision energies.

Gardenia fruit oil (GFO) is a new emerging edible woody oil with few investigations of its' refinement process. In this study, different degumming, deacidification and bleaching technologies were introduced for realizing moderate refining of the GFO based on the preservation of bioactive micronutrients. Firstly, a simple multi-stage solid phase extraction (SPE) combined with a lab- affordable HPLC-UV instrument was developed for determinations of several vital biological constituents, such as crocetin, geniposide, polyphenols, phytosterols and squalene in the GFO. Satisfactory limit of detection (LOD), limit of quantification (LOQ), recovery, intra-day and inter-day precision were obtained. Subsequently, changes of those phytochemicals during three types of degumming, followed by three kinds of deacidification and then three ways of bleaching were investigated, offering insightful suggestions for achieving moderate refining of the GFO. Finally, the refined GFO might be suggested as a potential functional edible oil with valuable micronutrients. To our knowledge, this is the first study investigating moderate refinement techniques for GFO, as well as developing novel methods for phytonutrients analysis in the GFO.

Tungsten (W), a toxic and hazardous pollutant, poses substantial risks to both aquatic life and human health. However, the available understanding of the migration properties of W in lake sediments under various habitats is still limited. This study was designed to evaluate variations in the concentrations of soluble W, manganese (Mn), and iron (Fe) in the summer season by applying a high-resolution Peeper sampling device. According to the results, soluble W concentrations and release fluxes were higher in the pore water of sediments in algae-dominated lake areas than in areas dominated by aquatic plants. This result indicates that the competition for adsorption between algae-derived dissolved organic matter and W, as well as the reductive dissolution caused by dissolved organic matter on Fe (III)/Mn (IV) (hydroxyl) oxides, contributes to the release of W from lake sediments. W uptake by aquatic plants and in-situ formation of Fe (III)/Mn (IV) (hydroxyl) oxides might be the primary factor that controls W release from lake sediments. Aquatic plants can effectively control W release from sediments. The findings of this work provide a scientific basis for the effective control of W release from shallow lake sediments.

Maintaining tissue homeostasis necessitates the coordinated efforts of various cell types to regulate inflammation. Endoplasmic reticulum (ER) stress, a hallmark of inflammation, exacerbates tissue pathology in various human diseases. Glutathione (GSH), a pivotal regulator of cellular redox balance, controls disulfide bond formation in the ER, thereby shielding cells from oxidative stress. In this study, we developed a two-photon fluorescent probe, ER-GSH, with specific ER targeting and demonstrated its high sensitivity and rapid response to GSH. Experiments conducted on BV2 cells and a mice model of neuroinflammation induced by scrap leather revealed that inflammatory reactions led to ER stress and a substantial reduction in GSH levels. Notably, the anti-inflammatory drug NS-398 effectively inhibited cell inflammation and ER stress by maintaining GSH levels. These findings underscore the potential therapeutic significance of modulating GSH levels to alleviate the impact of neuroinflammation.

The broad application of ionic liquids (ILs) has been hindered by uncertainties surrounding their ecotoxicity. In this work, a Quantitative Structure-Activity Relationship (QSAR) model was devised to predict the inhibition of ILs towards the activity of AChE, employing both Random Forest (RF) and eXtreme Gradient Boosting (XGBoost) machine learning approaches. Fourteen kings of essential molecular feature descriptors were screened from an initial roster of 244 descriptors through the application of a feature importance index and they showed a significant impact on the activity of AChE activity. The two models based solely on the 14 most critical molecular descriptors could maintain model's robustness and reliability. The correlation analysis between these 14 descriptors and the inhibition of AChE activity revealed the potential impact of the molecular characteristics on ILs toxicity. The results underscored the main influence of cations in ILs on the inhibitory activity towards the AChE enzyme. Specifically, cations exhibiting hydrophobicity properties were found to exert more potent inhibitory effects on the AChE enzyme. In addition, some other properties of the cations, such as the degree of branching, atomic weight and partial charge also modulated their inhibition potential. This study enhances the comprehension of the structure-activity relationship between ILs and AChE inhibition, providing a reference for designing safer and greener ILs.

It is well known that aquaculture can alter the microenvironments of lakes at sediment-water interface (SWI). However, the main mechanisms underlying the effects of aquaculture activities on arsenic (As) transformations are still unclear. In this context, the present study aims to investigate the variations in the sediment As contents in Yangcheng Lake, as well as to assess its chemical transformations, release fluxes, and release mechanisms. The results showed substantial spatial differences in the dissolved As concentrations in the sediment pore water. The As release fluxes at the SWI ranged from 1.32 to 112.09 μg/L, with an average value of 33.68 μg/L. In addition, the highest As fluxes were observed in the aquaculture areas. The transformation of crystalline hydrous Fe oxide-bound As to adsorbed-As in the aquaculture lake sediments increased the ability of As release. The Partial least squares path modeling results demonstrated the great contributions of organic matter (OM) to the As transformations by influencing the sediment microbial communities and Fe/Mn minerals. The changes in the As fractionation and competing adsorption increased the dissolved As concentrations in the 0-10 mm surface sediment. Non-specifically and specifically adsorbed As were the major sources of dissolved As in the sediments. Specifically, microbial reduction of As[V] and dissolution of Fe oxides increased the dissolved As concentrations at the SWI (20 to -20 mm). The results of the current study highlight the positive enhancement effects of aquaculture on As release from sediments.

The development of fluorescent probes capable of detecting abnormal changes in cellular mitochondrial viscosity is of great significance, as these changes have been connected to many diseases. In this study, the conventional tetraphenylethylene (TPE) molecule was modified to fabricate a novel near-infrared fluorescent, TTPB, which was then used to measure the mitochondrial viscosity. Due to the introduction of TPE and pyridine groups, TTPB had an AIE effect and mitochondrial targeting function. Meanwhile, TTPB was extremely sensitive to variations in viscosity for the twisted intramolecular charge transfer (TICT) phenomenon. The logarithm of fluorescence intensity (logI620) of the probe demonstrated an excellent linear connection with the logarithm of viscosity (logη) in the viscosity range of 1.2 ∼ 956.0 cP, indicating the probe could quantitatively detect viscosity. Moreover, TTPB was able to visually track autophagy in addition to detecting the mitochondrial viscosity in the inflammatory cell model. These results showed that the probe was anticipated to be employed for the early diagnosis of related diseases.

Abnormal viscosity and excessive superoxide anion (O2•-) levels in living cells often cause a series of biological dysfunction and oxidative damage. However, a great challenge remains in quickly and conveniently detecting the viscosity and O2•- levels in living cells. Herein, we fabricated a versatile aggregation-induced emission (AIE) probe with mitochondria targeting, DTPB, for dual-imaging of viscosity and O2•- level in living cells with two different channels. The obtained DTPB contained a diphenyl phosphinic acid unit responsive to O2•-, a unit with twisted intramolecular charge trans (TICT) function responsive to viscosity, and a pyridine cation unit with mitochondria targeting. The results showed that DTPB exhibited a remarkable response to viscosity with a near-infrared emission peak at 671 nm and was highly sensitive to O2•- levels with an emission peak at 587 nm. The dual-channel probe has great application prospects in the visual diagnosis of cancer and related diseases.

Since lipid oxidation often causes serious food safety issues worldwide, determination of oil's oxidative deterioration becomes quite significant, which still calls for efficient analytical methods. In this work, high-pressure photoionization time-of-flight mass spectrometry (HPPI-TOFMS) was firstly introduced for rapid detection of oxidative deterioration in edible oils. Through non-targeted qualitative analysis, oxidized oils with various oxidation levels were successfully discriminated for the first time by coupling HPPI-TOFMS with the orthogonal partial least squares discriminant analysis (OPLS-DA). Furthermore, by targeted interpretation of the HPPI-TOFMS mass spectra and the subsequent regression analysis (signal intensities vs TOTOX values), good linear correlations were observed for several predominant VOCs. Those specific VOCs were promising oxidation indicators, which would play important roles as TOTOX to judge the oxidation states of tested samples. The proposed HPPI-TOFMS methodology can be used as an innovative tool for accurate and effective assessment of lipid oxidation in edible oils.

In recent years, reflecting the degree of cellular inflammation through in situ monitoring of nitric oxide using fluorescence sensing has received much attention due to many merits such as non-invasiveness and easy operation. In particular, two-photon excitation microscopy can significantly improve the imaging resolution and visualization time. In the meantime, a ratiometric-based nitric oxide fluorescent sensor can avoid the interference of many factors, including light source intensity, solvent scattering degree, solvent color, solvent viscosity, probe distribution, and instrument performance, and improve the accuracy of the result. However, the mutual interference of two emission peaks is still an issue restricting the development of this field. In this work, the Rh-NO-F dye obtained by modifying the rhodol dye with benzothiazole exhibited excited state intramolecular proton transfer (ESIPT) in the closed ring state. In the open ring state, however, the emission wavelength can be significantly red-shifted by increasing the degree of dye conjugation. By introducing o-phenylenediamine, the recognition domain of NO, we successfully designed and synthesized a ratiometric two-photon NO fluorescent probe, Rh-NO-P, which showed a 154 nm increase in the maximum emission wavelength before and after the response and almost no interference between the two emission peaks. Confocal imaging showed that the probe could achieve in situ detection of exogenous NO fluctuations in cells. The probe was also successfully applied to detect the changes in NO content during wound healing in mice.