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Herein, we report a visible light-induced diheteroarylation reaction of [1.1.1]propellane to synthesize 1,3-diheteroaryl bicyclo[1.1.1]pentanes (BCPs). In this approach, heteroaryl radicals are generated from heteroaryl halides via photocatalysis and subsequently added to [1.1.1]propellane. The in situ generated BCP radicals are then trapped by various heterocycles to furnish 1,3-diheteroaryl BCPs. Notably, this strategy features metal-free, mild conditions and utilizes inexpensive catalyst. For the first time, the diheteroarylation of [1.1.1]propellane could be achieved via a radical strategy, allowing for the efficient synthesis of 1,3-diheteroaryl BCPs with various applications in organic and medicinal chemistry.

In recent years, organic semiconductor (OSC) ultrathin films and their solution-processed organic field-effect transistors (OFETs) have garnered attention for their high flexibility, light weight, solution processability, and tunable optoelectronic properties. These features make them promising candidates for next-generation optoelectronic applications. An ultrathin film typically refers to a film thickness of less than 10 nm, i.e., several molecular layers, which poses challenges for OSC materials and solution-processed methods. In this paper, first we introduce the carrier-transport regulation mechanism under ultrathin limits. Second, we summarize various solution-processed techniques for OSC ultrathin films and elucidate advances in their OFETs performance, such as enhanced or maintained mobilities, improved switching ratios, reduced threshold voltages, and minimized contact resistance. The relationship between the ultrathin-film thickness, microstructure of various OSCs (small molecules and polymers), and device performance is discussed. Third, we explore the recent application of OSC ultrathin-film-based OFETs, such as gas sensors, biosensors, photodetectors, and ferroelectric OFETs (Fe-OFETs). Finally, the conclusion is drawn, and the challenges and prospects of ultrathin OSC transistors are presented. Nowadays, research on ultrathin films is still in its early stages; further experience in precise film deposition control is crucial to advancing research and broadening the scope of applications for OSC ultrathin devices.

The optimization of hit compounds into drug candidates is a pivotal phase in drug discovery but often hampered by cumbersome manual synthesis of derivatives. While automated organic molecule synthesis has enhanced efficiency, safety, and cost-effectiveness, achieving fully automated multistep synthesis remains a formidable challenge due to issues such as solvent and reagent incompatibilities and the accumulation of side-products. We herein demonstrate an automated solid-phase flow platform for synthesizing α-keto-amides and nitrile peptidomimetics, guided by docking simulations, to identify potent broad-spectrum antiviral leads. A compact parallel synthesizer was built in-house, capable of producing 5 distinct molecules per cycle; 525 reactions could be finished within three months to generate 42 derivatives for a structure-activity relationship (SAR) investigation. Among these, ten derivatives exhibited promising target inhibitory activity (IC 50 < 100 nM) including two with antiviral activity (EC 50 < 250 nM). The platform, coupled with digital chemical recipe files, offers rapid access to a wide range of peptidomimetics, serving as a valuable reservoir for broad-spectrum antiviral candidates. This automated solid-phase flow synthesis approach expedites the generation of previously difficult complex molecular scaffolds. By integration of SPS-flow synthesis with medicinal chemistry campaign, >10-fold target inhibitory activity was achieved from a small set of derivatives, which indicates the potential to shift the paradigm of drug discovery.

The accurate understanding of mass transfer in molten salt contributes to revealing the reaction mechanism and advancing the technologies. The existence of notable natural convection effects has been demonstrated in our previous studies, even though the driving forces for such a high natural convection are still not clear. Herein, we showed that the intense natural convection in molten salts resulted from severe heat dissipation through the electrodes (or the system). With an adiabatic design, natural convection effects were significantly suppressed in molten LiCl-KCl. The derived value of the natural convection layer (δ conv ) ranged from 190 to 250 μm in molten LiCl-KCl containing a redox couple (e.g., SmCl 3 , EuCl 3 , and CrCl 3 ), comparable to those in aqueous solutions. The values of δ conv in LiCl-KCl-173 mM CrCl 3 increased to ∼360 μm due to the change in salt viscosity. The density-driven convection became dominant under a high redox concentration, and the increasing working temperature had no apparent effect on the natural convection effects because of the adiabatic design.

Photothermal therapy (PTT) is a promising technology that can achieve the thermal ablation of tumors and induce immunogenic cell death (ICD). However, relying solely on the antitumor immune responses caused by PTT-induced ICD is insufficient to suppress tumor metastasis and recurrence effectively. Fortunately, multifunctional nanoformulation-based synergistic photothermal immunotherapy can eliminate primary and metastatic tumors and inhibit tumor recurrence for a long time. Herein, we select polydopamine (PDA) nanoparticles to serve as the carrier for our nanomedicine as well as a potent photothermal agent and modulator of macrophage polarization. PDA nanoparticles are loaded with the insoluble immune adjuvant Imiquimod (R837) to construct PDA(R837) nanoformulations. These straightforward yet highly effective nanoformulations demonstrate excellent performance, allowing for successful triple-negative breast cancer (TNBC) treatment through synergistic photothermal immunotherapy. Moreover, experimental results showed that PDA(R837) implementation of PTT is effective in the thermal ablation of primary tumors while causing ICD and releasing R837, further promoting dendritic cell (DC) maturation and activating the systemic antitumor immune response. Furthermore, PDA(R837) nanoformulations inhibit tumor metastasis and recurrence and achieve M1 phenotype macrophage polarization, achieving long-term and excellent antitumor efficacy. Therefore, the structurally simple PDA(R837) nanoformulations provide cancer treatment and have excellent clinical translational application prospects.

The development of stimulus-responsive and amplification-based strategies is crucial for achieving improved spatial specificity and enhanced sensitivity in tumor molecular imaging, addressing challenges such as off-tumor signal leakage and limited biomarker content. Therefore, a cyclically activated enzymatic biosensor based on the modification of an AP site within a tetrahedral framework DNA (AP-tFNA) was rationally developed for tumor cell-specific molecular imaging using the endogenous enzyme apurinic/apyrimidinic endonuclease 1 (APE1) as a target, exhibiting superior spatial specificity and high sensitivity. APE1, which predominantly localizes within the nucleus in normal cells but exhibits cytosolic and nucleus expression in cancer cells, can specifically recognize and cleave the AP site in AP-tFNA, resulting in the separation of the fluorophore and quenching group, thereby inducing a fluorescence signal. Additionally, upon completion of the excision of one AP site in AP-tFNA, APE1 is released, thereby initiating a subsequent cycle of hydrolytic cleavage reactions. The experimental results demonstrated that AP-tFNA enables precise differentiation of tumor cells both in vitro and in vivo . In particular, the AP-tFNA can monitor drug resistance in neuroblastoma cells and classify the risk for neuroblastoma patients at the clinical plasma level.

Carbon fiber reinforced polymers (CFRPs, or composites) are increasingly replacing traditional manufacturing materials used in the automobile, aerospace, and energy sectors. With this shift, it is vital to develop end-of-life processes for CFRPs that retain the value of both the carbon fibers and the polymer matrix. Here we demonstrate a strategy to upcycle pre- and postconsumer polystyrene-containing CFRPs, cross-linked with unsaturated polyesters or vinyl esters, to benzoic acid. The thermoset matrix is upgraded via biocatalysis utilizing an engineered strain of the filamentous fungus Aspergillus nidulans , which gives access to valuable secondary metabolites in high yields, exemplified here by (2 Z ,4 Z ,6 E )-octa-2,4,6-trienoic acid. Reactions are engineered to preserve the carbon fibers with much of their sizing so that the isolated carbon fiber plies are manufactured into new composite coupons that exhibit mechanical properties comparable to those of virgin manufacturing substrates. In sum, this represents the first system to reclaim a high value from both the fiber fabric and polymer matrix of a CFRP.

Nonalcoholic fatty liver disease (NAFLD) causes significant global mortality and healthcare costs with no recommended pharmacological intervention for clinical management. Nuciferine (Nuc) is an alkaloid with aromatic rings, abundantly found in Nelumbo nucifera Gaertn . In this study, we explored the protective mechanisms of Nuc against hepatic steatosis and ferroptosis in NAFLD. High-fat diet (HFD) and healthy male ApoE -/- mice were used to induce NAFLD and a hypercholesterolemia model. Nuc was administered to the mice for four consecutive weeks from the ninth week. Various assessments, including histopathology, RNA sequencing, lipid metabolism, and ferroptosis-related protein expression, showed that Nuc alleviated hepatic steatosis and ferroptosis. We further showed that Nuc improves fatty acid accumulation and ferroptosis through the PPARα signaling pathway in mice and RSL3-treated AML-12 cells. The PPARα inhibitor GW6471 blocked Nuc's protective effects, leading to excess accumulation of iron ions. Thus, Nuc may be a potential therapeutic agent for NAFLD.

Buddlejasaponin IVb (BJP-IVb), a triterpenoid saponin derived from Pleurotus ostreatus , is abundant in bioactive constituents. However, its potential therapeutic benefits and underlying mechanism of action against ulcerative colitis (UC) remain elusive. Studies performed using a mouse model of colitis caused by dextran sulfate sodium showed that BJP-IVb helped reduce symptoms of UC, such as weight loss, a higher disease activity index, shorter colon length, and colon damage. It also repaired the intestinal barrier function and suppressed inflammation. BJP-IVb activated the Nrf2/HO-1 antioxidant pathway, inhibited ferroptosis, and affected protein expression and oxidative indicators. The combined use of BJP-IVb and Nrf2 inhibitor ML385 negated the effects of BJP-IVb. In Nrf2-KO mice, the protective effects of BJP-IVb were reversed. BJP-IVb inhibited ferroptosis via the Nrf2/GPX4 axis and alleviated gut microbiota dysbiosis. In conclusion, our research validates the therapeutic and protective efficacy of BJP-IVb on ulcerative colits. Additionally, it offers new perspectives on preventing colitis by focusing on the metabolism of gut microbiota using natural substances.

Microelectrodes have transformed our understanding of spatiotemporal responses to electrical stimulation. However, biological signals are often molecular, complicating the capture of intricate chemical signals. The microfluidic chip developed in this paper accurately measures droplet volume by using impedance analysis. The utilization of droplet volume as a feedback signal for precise microsampling pressure control ensures that microsampling remains unaffected by droplet volume influence. Once the microsampling is complete, chemiluminescence detection enables high temporal resolution and continuous and sensitive monitoring of chemical information within the droplets. Experimental verification shows that the chip can avoid volume influence through impedance feedback, achieving consistent and stable microampling at the nanoliter level (0-3 nL). In just 0.3 s, it can perform sensitive chemiluminescence detection of H 2 O 2 and glucose within droplets. The linear detection ranges for these analytes are 10-50,000 and 20-600 μM, respectively, with the limit of detection being 0.648 and 0.334 μM. The significance of this chip lies in its ability to reveal changes in both electrical and chemical signals during transient biological processes. Its potential applications are numerous, encompassing a wide range of emerging areas such as single-cell analysis, cell communication, and cellular immunity.

Recent advances in machine-learning-based electronic coarse graining (ECG) methods have demonstrated the potential to enable electronic predictions in soft materials at mesoscopic length scales. However, previous ECG models have yet to confront the issue of chemical transferability. In this study, we develop chemically transferable ECG models for polythiophenes using graph neural networks. Our models are trained on a data set that samples over the conformational space of random polythiophene sequences generated with 15 different monomer chemistries and three different degrees of polymerization. We systematically explore the impact of coarse-grained representation on ECG accuracy, highlighting the significance of preserving the C-β coordinates in thiophene. We also find that integrating unique polymer sequences into training enhances the model performance more efficiently than augmenting conformational sampling for sequences already in the training data set. Moreover, our ECG models, developed initially for one property and one level of quantum chemical theory, can be efficiently transferred to related properties and higher levels of theory with minimal additional data. The chemically transferable ECG model introduced in this work will serve as a foundation model for new classes of chemically transferable ECG predictions across chemical space.

New photochemical approaches to 2,3-fused quinazolinones and dihydroquinazolinones are disclosed. The intramolecular hydrocyclization proceeds in moderate to excellent yields across diverse alkenes with high regioselectivity and diastereocontrol. Mechanistic studies indicated that the radical cascade processes involve thiophenol acting as single-electron transfer and hydrogen atom transfer reagents. The success of the gram-scale synthesis proves the strategy can be used for practical applications.

Myocardial ischemia-reperfusion (IR) injury is a severe rhythmic disease with a high prevalence in the early morning. IR injury has a significant circadian rhythm in reactive oxygen species (ROS) and inflammation levels. The development of rhythmic drugs has become a priority in myocardial IR injury. In this study, resveratrol (RES) and proanthocyanidins (OPC) were utilized to design nanoparticles (NPs), with hyaluronic acid (HA) as the core, grafted with MMP-targeting peptides to improve delivery to injured myocardial regions (HA-RES-OPC-MMP NPs). NPs significantly scavenged ROS, attenuated inflammation, and activated the rhythm gene. Notably, the difference in therapeutic effects on myocardial IR injury in mice at Zeitgeber time (ZT)1 and ZT13 confirms that NPs are rhythm-dependent drugs. At ZT13, echocardiographic and MRI confirm that IR injury in mice was not as severe as at ZT1, yet NPs were also less effective in treatment. Further, Per1/2 knockout mice confirmed the rhythm-dependent treatment of myocardial IR injury by NPs. Molecular studies have shown that rhythmic characteristics of inflammation and Sirt1 transcript levels are the main reasons for the different rhythmic therapeutic effects of NPs. Circadian rhythm-dependent treatment of HA-RES-OPC-MMP NPs has excellent potential for more precise treatment of myocardial IR injury in the future.

Proton nuclear magnetic resonance (NMR) relaxometry is proposed to determine the iron redox ratio of slag samples. It depends on the paramagnetic effect on bulk water relaxation times. Experiments have been carried out to calibrate the relationship between the concentration of Fe 3+ and Fe 2+ ions and the measured relaxation times on prepared standard samples. It is shown that Fe 2+ ions have very different effects on the relaxation times than Fe 3+ ions. For the solid slag samples, digestion in an acid was used to produce solutions with a pH of 1.0. Hydrogen peroxide (H 2 O 2 ) was then added to the digested samples to oxidize Fe 2+ ions to Fe 3+ ions. The concentration of Fe 2+ and Fe 3+ ions in solution can be calculated by measuring the relaxation times before and after oxidation. The Fe 3+ /∑Fe ratio of slag samples was also investigated by wet chemistry and 57 Fe Mössbauer spectroscopy and calculated by FactSage at the equilibrium state. The results obtained from different methods are consistent, indicating that this NMR relaxometry method is reliable.

3D printing of a flexible polyurethane elastomer is highly demandable for its potential to revolutionize industries ranging from footwear to soft robotics thanks to its exceptional design flexibility and elasticity performance. Nevertheless, conventional methods like fused deposition modeling (FDM) and vat photopolymerization (VPP) polyurethane 3D printing typically limit material options to thermoplastic or photocurable polyurethanes. In this research, a water-borne polyurethane ink was synthesized for direct ink writing (DIW) 3D printing through the incorporation of cellulose nanofibrils (CNFs), enabling direct printing of complex, monolithic elastomeric structures at room temperature that can maintain the designed structure. Additionally, a solvent-induced fast solidification (SIFS) method was introduced to facilitate room-temperature curing and enhance mechanical properties. The 3D-printed WPU structures demonstrated strong interfacial adhesion, exhibiting high ultimate tensile strength of up to 22 MPa and an elongation at break of 951%. The 3D-printed WPU structures also demonstrated outstanding resilience and durability, capable of enduring more than 100 cycles of compression and tension as well as withstanding vehicle crushing and heavy lifting. This method also shows suitability for 3D printing complex structures such as a vase and an octopus.

Incineration is a promising sustainable treatment method for solid waste. However, the ongoing revelation of new toxic pollutants in this process has become a controversial issue impeding its development. Thus, identifying and regulating high-risk pollutants emerge as pivotal strides toward reconciling this debate. In this study, we proposed a workflow aimed at establishing priority monitoring inventories for organic compounds emitted by industries involving full-component structural recognition, environmental behavior prediction, and emission risk assessment, specifically focusing on solid waste incineration (SWI). A total of 174 stack gas samples from 29 incinerators were first collected. Nontarget full organic recognition technology was then deployed to analyze these samples, and 646 organic compounds were identified. The characteristics, i.e., toxicity effects, toxicity concentrations, persistence, and bioaccumulation potential, of these compounds were assessed and ranked based on the TOXCAST database from the US Environmental Protection Agency and structural effect models. Combined with consideration of changes in seasons and waste types, a priority control inventory consisting of 28 organic pollutants was finally proposed. The risks associated with SWI across different regions in China and various countries were assessed, and results pinpointed that by controlling the priority pollutants, the average global emission risk attributed to SWI was anticipated to be reduced by 71.4%. These findings offer significant guidance for decision-making in industrial pollutant management, emphasizing the importance of targeted regulation and monitoring to enhance the sustainability and safety of incineration processes.

The integration of optoelectronic devices with reservoir computing offers a novel and effective approach to in-sensor computing. This work presents a hybrid digital-physical solution that leverages the high-performance poly[(bithiophene)-alternate-(2,5-di(2-octyldodecyl)-3,6-di(thienyl)-pyrrolyl pyrrolidone)] (DPPT-TT) organic polymer-based photodiodes for the hardware implementation of reservoir computing system. The photodiodes demonstrate nonlinear photoelectric responses, fading memory, and cyclical stability, in relation to the temporal information on light stimuli. These attributes enable effective mapping, historical context sensitivity, and consistent performance, with time-encoded inputs, which are particularly essential for accurate and continuous processing of time series data. The optoelectronic reservoir computing system with pulse width modulation (PWM) coding demonstrates impressive performance in the prediction of chaotic sequences, achieving a normalized root-mean-square error as low as 0.095 with optimized parameters. The DPPT-TT-based photodiodes and time-based coding offer a hardware-efficient solution for reservoir computing, significantly advancing Internet of Things applications.

Barocaloric materials hold great promise for next-generation solid-state cooling devices because of their green and efficient cooling performance. The insights into low-pressure-driven barocaloric materials are expected to pave the way for the widespread application of barocaloric refrigeration technology. Here, we reveal the low-pressure-driven large barocaloric effect (BCE) modulated by geometrical frustrations in Mn 3 Pt. The highest sensitivity to pressure of Mn 3 Pt in metal BCE materials results in an excellent temperature-change strength of 9.77 K 100 -1 MPa -1 . Neutron powder diffraction and first-principles calculations point out the dual effect of geometrical frustration on modulating the unusual BCE, which not only induces giant volume expansion by inspiring strong spin fluctuation and magnetic moment but also enhances the sensitivity of magnetic phase transition. The model of the dual effect of geometrical frustration in magnets with geometrical frustration is established, which will promote the research progress of barocaloric refrigeration devices.

To discover novel inhibitors of the complex I reduced nicotinamide adenine dinucleotide (NADH) oxidoreductase as fungicides, a series of 6-isothiazol-5-ylpyrimidin-4-amine-containing compounds were designed using a computer-aided pesticide design method and splicing of substructures from diflumetorim and isotianil. In vitro fungicidal bioassays indicated that compounds T17 - T24 showed high inhibitory activity against Rhizoctonia solani with an effective concentration (EC 50 ) value falling between 2.20 and 23.85 μg/mL, which were more active than or equivalent to the lead diflumetorim with its EC 50 of 19.80 μg/mL. In vivo antifungal bioassays demonstrated that, at a concentration of 200 μg/mL, T7 and T21 showed higher inhibition against Pseudoperonospora cubensis than all other compounds, while T23 exhibited the highest inhibition against Sphaerotheca fuliginea . T23 showed an approximately twofold lower inhibition potency against R. solani complex I NADH oxidoreductase than diflumetorim. Molecular docking and transcriptomic analyses indicated that T23 and diflumetorim both might share the same mode of action, targeting NADH oxidoreductase. T23 as a good fungicidal candidate against R. solani is worthy of further investigation.

The proliferation speed of live foodborne pathogens is fast. A small number of pathogens will have a great impact on food and the environment if positive samples are not detected timely. In this study, transparent porous hydrogel stir bars, modified by two different phages (corresponding to two different bacteria ( Escherichia coli and Hafnia sp )), have been developed for rapid detection of foodborne bacteria. A large number of samples can be analyzed simultaneously with a small animal live imager device to screen out the positive samples, while an adenosine triphosphate (ATP) bioluminescence sensor can be used to quantify the number of bacteria in the positive samples. The phage has good specificity and capture ability to bacteria, which makes the method highly sensitive. In addition, the use of multiple phages also enables the method to detect multiple bacteria simultaneously. The three-dimensional structure of the hydrogel allows it to modify more phages, and its transparent nature also allows the inside bioluminescence to be detected. Both can enhance the sensitivity of the detection. Finally, the reagents needed for bioluminescence, such as d-luciferin, can also be preencapsulated in the hydrogel, thus simplifying the detection step. Under the best conditions, the detection range of the method is 10 2 -10 8 CFU·mL -1 , and the limit of detection is 30 CFU·mL -1 within 11 min. The test results of actual samples show that there is no difference between using the method developed through this study and the traditional plate counting method, but the detection time is greatly shortened.

A common issue with supported metal catalysts is the sintering of metal nanoparticles, resulting in catalyst deactivation. In this study, we propose a theoretical framework for realizing a real-time simulation of the reactivity of supported metal nanoparticles during the sintering process, combining density functional theory calculations, microkinetic modeling, Wulff-Kaichew construction, and sintering kinetic simulations. To validate our approach, we demonstrate its feasibility on α-Al 2 O 3 (0001)-supported Ag nanoparticles, where the simulated sintering behavior and ethylene epoxidation reaction rate as a function of time show qualitative agreement with experimental observation. Our proposed theoretical approach can be employed to screen out the promising microstructure feature of α-Al 2 O 3 for stable supported Ag NPs, including the surface orientation and promoter species modified on it. The outlined approach of this work may be applied to a range of different thermocatalytic reactions other than ethylene epoxidation and provide guidance for the development of supported metal catalysts with long-term stability.

Near-infrared (NIR) persistent luminescence (PersL) materials have unique optical properties with promising applications in bioimaging and anticounterfeiting. However, their development is currently hindered by poor red-light-exciting ability. In this study, CaTiO 3 :Cr 0.001 ,Y 0.02 (CTCY) was synthesized with 650 nm-excited 772 nm NIR PersL. The Y 3+ doping in the Ca 2+ lattice plays a key role in the PersL property. A charge compensation mechanism was proposed, in which Cr 3+ in the Ti 4+ lattice was stabilized by Y 3+ -doping while oxygen vacancies were generated to store the excitation energy at the same time. A thermal ionization mechanism might elucidate the red-light-excited NIR PersL of CTCY, which benefits from the perovskite structure of CaTiO 3 . CTCY has 120 times more intense red-light-excited PersL than Zn 3 Ga 2 Ge 2 O 10 :Cr. Its potential applications in luminescence anticounterfeiting and bioimaging were demonstrated using a visible/NIR dual-channel PersL flower painting and a CTCY-labeled bone screw for in situ reactivable PersL imaging using red light illumination instead of X-ray, respectively. This study not only provides a new NIR PersL material but also will add to our understanding in developing other potential red-light- or even NIR-activable PersL materials with perovskite-like structures.

The Barbier reaction is a reductive-type addition of an aldehyde or ketone with an organic electrophile in the presence of a terminal metal reductant, providing a straightforward and efficient method for carbon-carbon bond formation. This reaction possesses the advantage of circumventing the preparation of moisture- and air-sensitive organometallic reagents. However, the catalytic Barbier reaction of ketones to construct tetrasubstituted stereogenic centers is largely underdeveloped, despite its great potential for accessing synthetically challenging chiral tertiary alcohol. Particularly, the leveraging of unactivated alkyl electrophiles as coupling components is still rarely exploited. Herein, we disclose a photoredox-assisted cobalt-catalyzed asymmetric alkylative Barbier-type addition reaction of ketones to address the aforementioned challenges, thereby allowing for the construction of highly congested tetrasubstituted carbon centers. The alkyl addition fragments could be either readily accessible unactivated alkyl halides or redox-active esters generated through a decarboxylative pathway. Both types of alkyl electrophiles include primary, secondary, and tertiary ones, thus affording diverse enantioenriched tertiary alcohols with a broad substrate scope. This enantioselective protocol is applied for the expedient synthesis of core structure of Sofdra , a very recent FDA-approved drug in 2024. The newly developed bisoxazolinephosphine (NPN) ligand enables high enantioselectivity in this asymmetric reductive addition process.

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

Precise on-site monitoring of alkylresorcinols, a vital biomarker, is crucial for verifying whole wheat foods and accurately quantifying the whole wheat content in various consumer and industrial products. Herein, for the first time, we introduce a novel ratiometric fluorescence sensor (CDs@ZIF-8/CdTe@MIP) for ultrasensitive and selective detection of alkylresorcinols. 5-Heneicosylresorcinol (C21:0 AR), the primary alkylresorcinol homologue in whole wheat grains, was selected as the target analyte. This analyte was specifically and selectively recognized by the incorporation of a molecularly imprinted polymer (MIP) layer. Within this nanoreactor, blue-emitting carbon dots embedded in zeolitic imidazolate framework-8 (CDs@ZIF-8) and orange-emitting CdTe quantum dots served as the self-calibration signal and response signal, respectively. Exploiting a photoinduced electron transfer effect between CdTe and C21:0 AR, the established fluorescence sensor exhibited remarkable sensing performance, offering wide linear responses in 0.005-1 μg·mL -1 and 1-80 μg·mL -1 concentration ranges, and achieving a low detection limit of 1.14 ng·mL -1 . The proposed assay effectively detected C21:0 AR in real samples, including 8 whole wheat foods and 19 whole wheat grains, demonstrating good recoveries and relative standard deviation. Furthermore, an intelligent sensing platform was established by integrating CDs@ZIF-8/CdTe@MIP with a smartphone-assisted device, thus validating the feasibility of visual and on-site monitoring of C21:0 AR. Because of its rapid response, portability, cost-effectiveness, superior sensitivity, and high selectivity, the proposed sensor serves as a reliable method for the analysis of C21:0 AR, thus having substantial potential for on-site monitoring of whole wheat foods.

Controlling gas admission by regulating pore accessibility in porous materials has been a topic of extensive research. Recently, the electric field (E-field) has emerged as an external stimulus to alter the adsorption behavior of some microporous adsorbents. However, the mechanism behind this phenomenon is not yet fully understood. Here, we demonstrate the crucial role of the trapdoor cations of zeolite molecular sieves in E-field-regulated gas adsorption. The E-field activation caused framework expansion and cation deviation, significantly reducing the energy barrier for gas molecules passing through the pore aperture gated by the trapdoor cation. This led to an increase in the N 2 adsorption capacity of ZSM-25 and a 60% improvement in N 2 /CH 4 selectivity in the quest for nitrogen rejection for natural gas processing. By combining experimental and computational approaches, we elucidated the influence of E-field activation as a concurrent effect of the reduced heat of adsorption caused by framework expansion and the decrease in the energy barrier resulting from promoted cation oscillation. These findings pave the way for the material design of E-field-regulated adsorption and its application in molecular separation.

The addition of C-H bonds to isocyanates catalyzed by transition metals is a highly auspicious methodology for providing synthetically and biologically important amides. However, the substrates are limited to C(sp 2 )-H bonds. In this work, an efficient manganese(I)-catalyzed direct addition reaction of C(sp 3 )-H bonds of 8-methylquinolines to aryl isocyanates has been developed, leading to the synthesis of various α-quinolinyl amide compounds in moderate to high yields. The reaction has a broad range of substrates and a good functional group tolerance. A possible mechanism is proposed based on the experimental results.

Antibiotic residues have been found in several aquatic ecosystems as a result of the widespread use of antibiotics in recent years, which poses a major risk to both human health and the environment. At present, photocatalytic degradation is the most effective and environmentally friendly method. Titanium silicon molecular sieve (TS-1) has been widely used as an industrial catalyst, but its photocatalytic application in wastewater treatment is limited due to its small pores and few active sites. In this paper, we report a method for preparing multistage porous TS-1 with a high specific surface area by alkali treatment. In the photocatalytic removal of CIP (ciprofloxacin) antibiotic wastewater experiments, the alkali-treated catalyst showed better performance in terms of interfacial charge transfer efficiency, which was 2.3 times higher than that of TS-1 synthesized by the conventional method, and it was found to maintain better catalytic performance in the actual water source. In addition, this research studied the effects of solution pH, contaminant concentration, and catalyst dosage on CIP degradation, while liquid chromatography-mass spectrometry (LC-MS) was used to identify intermediates in the degradation process and infer possible degradation pathways and the toxicity of CIP, and its degradation product was also analyzed using ECOSAR 2.2 software, and most of the intermediates were found to be nontoxic and nonharmful. Finally, a 3:5:1 artificial neural network model was established based on the experiments, and the relative importance of the influence of experimental conditions on the degradation rate was determined. The above results confirmed the feasibility and applicability of photocatalytic treatment of wastewater containing antibiotics using visible light excitation alkali post-treatment TS-1, which provided technical support and a theoretical basis for the photocatalytic treatment of wastewater containing antibiotics.

Socioeconomic inequalities in the exposome have been found to be complex and highly context-specific, but studies have not been conducted in large population-wide cohorts from multiple countries. This study aims to examine the external exposome, encompassing individual and environmental factors influencing health over the life course, and to perform dimension reduction to derive interpretable characterization of the external exposome for multicountry epidemiological studies. Analyzing data from over 25 million individuals across seven European countries including 12 administrative and traditional cohorts, we utilized domain-specific principal component analysis (PCA) to define the external exposome, focusing on air pollution, the built environment, and air temperature. We conducted linear regression to estimate the association between individual- and area-level socioeconomic position and each domain of the external exposome. Consistent exposure patterns were observed within countries, indicating the representativeness of traditional cohorts for air pollution and the built environment. However, cohorts with limited geographical coverage and Southern European countries displayed lower temperature variability, especially in the cold season, compared to Northern European countries and cohorts including a wide range of urban and rural areas. The individual- and area-level socioeconomic determinants (i.e., education, income, and unemployment rate) of the urban exposome exhibited significant variability across the European region, with area-level indicators showing stronger associations than individual variables. While the PCA approach facilitated common interpretations of the external exposome for air pollution and the built environment, it was less effective for air temperature. The diverse socioeconomic determinants suggest regional variations in environmental health inequities, emphasizing the need for targeted interventions across European countries.

Bacteria can cause infectious diseases even at ultralow concentrations (<1 CFU/mL). It is important to rapidly identify bacterial contamination at ultralow concentrations. Herein, FITC-labeled gelatinase-sensitive nanoparticles (GNPs@FITCs) and NFM@GNP@FITCs are designed and fabricated as ultralow concentration bacteria detection platforms based on an enzymatic cascade reaction-amplifying strategy. Bacterial secretions could trigger the dissociation of GNPs@FITCs to release FITC, with gelatinase used as the model secretion. The detectable signal of ultralow concentration bacteria could be amplified effectively by the gelatinase-triggered cascade reaction. Bacterial concentration was evaluated by the change in fluorescence density. The results showed that the GNPs@FITCs and NFM@GNP@FITCs could be used for identifying bacterial contamination qualitatively, even when the bacterial contamination is lower than 1 CFU/mL. Moreover, the method has better timeliness and convenience, when compared with national standards. As solid films, NFM@GNP@FITCs have better long-term storage stability than GNPs@FITCs. The potential applications of GNPs@FITC and NFM@GNP@FITCs were proved by detecting pathogenic bacteria in food. All the results showed that the method has great potential for screening pathogenic bacterial contamination qualitatively.

A highly efficient Ru-catalyzed asymmetric hydrogenation of α,β-unsaturated γ-lactams has been developed by using a C 2 -symmetric ruthenocenyl phosphine-oxazoline as the chiral ligand. This method achieves the enantioselective synthesis of chiral β-substituted γ-lactams in high yields and with excellent enantioselectivities (up to 99% yield with 99% ee). Mechanistic studies based on detailed control experiments and computational investigation revealed that the cationic Ru-complex acts as the active catalytic species; the protonation process of the oxa-π-allyl-Ru complex, which is formed by the migratory insertion of the C=C double bond to the Ru-H bond (the stereocontrolling step) followed by an isomerization process, is the rate-determining step, and the existence of PPh 3 is crucial for the highly efficient catalytic behavior. The protocol provides a straightforward and practical pathway for the synthesis of key intermediates for several chiral drugs and bioactive compounds, particularly for the 150 kg-scale industrial production of Brivaracetam, an antiepileptic drug that shows 13-fold more potent binding to the synaptic vesicle protein 2A compared with the well-known Levetiracetam.

Oil pollution poses a major threat to the ecosystem. Therefore, it is necessary to develop a material that can separate oil and water efficiently. Fabrics have a wide range of applications due to their economic simplicity and degradability. However, the existing methods of preparing superhydrophobic fabrics are complicated and energy-consuming, which are difficult to meet the concept of green and sustainable development. Moreover, various modified fabrics are less stable in harsh environments and do not have the ability to efficiently separate oil and water over a long period of time. In this paper, superhydrophobic zirconium dioxide (ZrO 2 ) obtained from the modification of stearic acid was loaded onto the fabric surface using the adhesive properties of PDMS, resulting in the preparation of superhydrophobic/superoleophilic STA-ZrO 2 fabrics. The fabric is made without involving time-consuming and energy-consuming heating, and it offers efficient oil-water separation, good stability and excellent recyclability. Truly in line with the concept of sustainable development.

Lipid droplets (LDs) are dynamic subcellular organelles that participate in various physiological processes, and their abnormality can also lead to various diseases. Tracing the dynamics of LDs in living cells will be valuable for understanding cell physiological states. Here, we employed a structured light illumination super-resolution imaging assisted with a carbonized polymer dot (CPD)-based fluorescence nanoprobe to track the travel paths of LDs and other organelles. The CPDs we developed are highly biocompatible with living cells and exhibit a highly sensitive response to solvent polarity, allowing for high specificity in staining LDs in living cells. Aided by these nanoprobes, we successfully observed many real-time LD-involved dynamics in living cells, such as intracellular LD interactions, communications with other organelles, and dynamic behaviors under external stimuli (oxidative stress inducer). These studies deepen our comprehension of the physiological role of LDs and drive the advancement of super-resolution fluorescent probes., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

An environmentally friendly electrochemical strategy for the synthesis of SCF 3 -containing oxindoles was developed. This electrochemical transformation was accomplished through a cascade trifluoromethylthiolation/cyclization of N -acrylamides with AgSCF 3 , obviating the requirement for external oxidants. A variety of functional groups were well tolerated in this transformation.

Jinhua finger citron is one of the traditional specialties of Jinhua with a long history of cultivation. The current study highlighted the advantages of using the quality by design approach to optimize the ultrasonic-assisted distillation extraction of Jinhua finger citron essential oil. The yield of Jinhua finger citron essential oil was regarded as a potential critical quality attribute. Potential critical process parameters were screened by the definitive screening design. Finally, the design space of the essential oil extraction process was constructed. The optimal operating space included an auxiliary NaCl concentration range of 9-12.00%, a soak temperature range of 30-50 °C, a distillation time range of 3.5-4.00 h, an ultrasonic power range of 200-300 W, a solid-liquid ratio range of 1:3-1:3.5, and a soak time range of 40-80 min. On this basis, the relative density, refractive index, and pH values of different batches of Jinhua finger citron essential oil were checked. The involved batches were analyzed by gas chromatography (GC), and gas chromatographic fingerprints were established by identifying major compounds, including d-limonene, γ-terpinene, and 5,7-dimethoxycoumarin. Based on the "quality by design" strategy, the extraction process of Jinhua finger citron essential oil established in this study was robust, reliable, and flexible., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The development of nontoxic antifouling coatings in static marine environments is urgent. Herein, the successful synthesis of sulfobetaine borneol fluorinated polymers (PEASBF) by a free radical polymerization method is reported. The PEASBF coatings exhibit outstanding antifouling activity, which effectively resists the adhesion of Bovine serum albumin (FITC-BSA adhesion rate: 0.5%), Pseudomonas sp . (Biofilm: 1.3 absorbance) and Navicula sp. (Diatom attachment rate: 33%). More importantly, the PEASBF coatings display outstanding fouling release properties, achieving a release rate of 98% for Navicula sp. , and the absorbance of the Pseudomonas sp . biofilm is only 0.2 under 10 Pa shear stress. XPS and MD studies showed that the fluorinated/isobornyl groups induce more sulfobetaine groups to migrate toward polymer surfaces for intensify antifouling. Additionally, the chiral stereochemical structure of borneol enhances antifouling and fouling release ability of amphiphilic polymers. Therefore, the PEASBF has the potential for static marine antifouling applications.

In situ self-assembly in living systems is referred to as the processes that regulate assembly by stimuli-responsive reactions at target sites under physiological conditions. Due to the advantages of precisely forming well-defined nanostructures at pathological lesions, in situ-formed assemblies with tailored bioactivity are promising for the development of next-generation biomedical agents. In this Perspective, we summarize the progress of in situ self-assembly of peptides in living cells with an emphasis on the state-of-the-art strategies regulating assembly processes, establishing complexity within assembly systems, and exploiting their applications in biomedicines. We also provide our forward conceiving perspectives on the challenges in the development of in situ assembly in living cells to demonstrate its great potential in creating biomaterials for healthcare in the future.

Identifying causative toxicants in mixtures is critical, but this task is challenging when mixtures contain multiple chemical classes. Effect-based methods are used to complement chemical analyses to identify toxicants, yet conventional bioassays typically rely on an apical and/or single endpoint, providing limited diagnostic potential to guide chemical prioritization. We proposed an event-driven taxonomy framework for mixture risk assessment that relied on high-throughput screening bioassays and toxicant identification integrated by deep learning. In this work, the framework was evaluated using chemical mixtures in sediments eliciting aryl-hydrocarbon receptor activation and oxidative stress response. Mixture prediction using target analysis explained <10% of observed sediment bioactivity. To identify additional contaminants, two deep learning models were developed to predict fingerprints of a pool of bioactive substances (event driver fingerprint, EDFP) and convert these candidates to MS-readable information (event driver ion, EDION) for nontarget analysis. Two libraries with 121 and 118 fingerprints were established, and 247 bioactive compounds were identified at confidence level 2 or 3 in sediment extract using GC-qToF-MS. Among them, 12 toxicants were analytically confirmed using reference standards. Collectively, we present a "bioactivity-signature-toxicant" strategy to deconvolute mixtures and to connect patchy data sets and guide nontarget analysis for diverse chemicals that elicit the same bioactivity.

Salmonella enterica serovar Typhimurium ( S. Typhimurium) is a common foodborne enteric pathogen that infects humans or mammals and colonizes the intestinal tract primarily by invading the host following ingestion. Meanwhile, ClpV is a core secreted protein of the bacterial type VI secretion system (T6SS). Because elucidating ClpV's role in the pathogenesis of T6SS is pivotal for revealing the virulence mechanism of Salmonella , in our study, clpV gene deletion mutants were constructed using a λ-red-based recombination system, and the effect of clpV mutation on SL1344's pathogenicity was examined in terms of stress resistance, motility, cytokine secretion, gut microbiota, and a BALB/c mouse model. Among the results, ClpV affected SL1344's motility and was also involved in cell invasion, adhesion, and intracellular survival in the MDBK cell model but did not affect invasion or intracellular survival in the RAW264.7 cell model. Moreover, clpV gene deletion significantly reduced the transcription levels of GBP2b, IFNB1, IL-6, NLRP3, NOS2, and TNF-α proinflammatory factor levels but significantly increased transcription levels of IL-4 and IL-10 anti-inflammatory factors. Last, ClpV appeared to closely relate to the pathogenicity of S. Typhimurium in vivo , which can change the gut environment and cause dysbiosis of gut microbiota. Our findings elucidate the functions of ClpV in S . Typhimurium and illustrating interactions between T6SS and gut microbiota help to clarify the mechanisms of the pathogenesis of foodborne diseases.

Cobalt phosphide has received much attention as an efficient catalyst for electrocatalytic hydrodechlorination (EHDC). However, the active species proton hydrogen (H*) is consumed by the hydrogen evolution reaction (HER). Herein, we report a crystal regulation strategy for cobalt phosphate/graphitic nanocarbon/nickel foam (CoPO/GC/NF) catalysts applied for the EHDC of 2,4-dichlorophenoxyacetic acid (2,4-D). Characterization revealed that during the high-temperature phosphatization process, CoPO/GC/NF catalysts developed Co(PO 3 ) 2 @CoP heterojunctions, enhancing charge transfer at the electrolyte-catalyst interface and water dissociation. The interaction between Co(PO 3 ) 2 and CoP induced the reconstitution of CoP into the Co-OH species, which facilitated the production of H* by accelerating the Volmer step, enhancing EHDC activity. Furthermore, Co(PO 3 ) 2 species improve the catalyst tolerance, with CoPO/GC/NF(450) maintaining over 71% yield of phenoxyacetic acid (PA) in continuous testing for up to 80 h under high-salt conditions. This work clarifies the surface transformation process of CoP/GC/NF during hydrodechlorination and demonstrates great potential for chlorophenol wastewater remediation.

Phytoene desaturase (PDS) is a key rate-limiting enzyme in the carotenoid biosynthesis pathway. Although commercial PDS inhibitors have been developed for decades, it remains necessary to develop novel PDS inhibitors with higher bioactivity. In this work, we used the scaffold hopping and linker modification approaches to design and synthesize a series of compounds ( 7a - 7o , 8a - 8l , and 14a - 14d ). The postemergence application assay demonstrated that 8e and 7e separately showed the best herbicidal activity at 750 g a.i./ha and lower doses (187.5 g, 375g a.i./ha) without no significant toxicity to maize and wheat. The surface plasmon resonance revealed strong binding affinity between 7e and Synechococcus PDS ( Syn PDS). The HPLC analysis confirmed that 8e at 750 g a.i./ha caused significant phytoene accumulation in Arabidopsis seedlings. This work demonstrates the efficacy of structure-guided optimization through scaffold hopping and linker modification to design potent PDS inhibitors with enhanced bioactivity and crop safety.

Despite significant progress achieved in artificial self-sorting in solution, operating self-sorting in the body remains a considerable challenge. Here, we report an in vivo self-sorting peptide system via an in situ assembly evolution for combined cancer therapy. The peptide E3C16-SS-EIY consists of two disulfide-connected segments, E3C16SH and SHEIY , capable of independent assembly into twisted or flat nanoribbons. While E3C16-SS-EIY assembles into nanorods, exposure to glutathione (GSH) leads to the conversion of the peptide into E3C16SH and SHEIY , thus promoting in situ evolution from the nanorods into self-sorted nanoribbons. Furthermore, incorporation of two ligand moieties targeting antiapoptotic protein XIAP and organellar endoplasmic reticulum (ER) into the self-sorted nanoribbons allows for simultaneous inhibition of XIAP and accumulation surrounding ER. This leads to the cytotoxicity toward the cancer cells with elevated GSH levels, through activating caspase-dependent apoptosis and inducing ER dysfunction. In vivo self-sorting of E3C16-SS-EIY decorated with ligand moieties is thoroughly validated by tissue studies. Tumor-bearing mouse experiments confirm the therapeutic efficacy of the self-sorted assemblies for inhibiting tumor growth, with excellent biosafety. Our findings demonstrate an efficient approach to develop in vivo self-sorting systems and thereby facilitating in situ formulation of biomedical agents.

Two-dimensional transition metal carbides/nitrides (MXenes) have shown great promise in various applications. However, mass production of MXenes suffers from the excessive use of toxic fluorine-containing reagents. Herein, a new method was validated for synthesizing MXenes from five MAX ceramics. The method features a minimized (stoichiometric) dosage of F-containing reagent (NaBF 4 ) and polyols (glycerol, erythritol, and xylitol) as the reaction solvent. Due to the sweetness of polyols and the low environmental impact, we refer to this method as a "sweet" synthesis of MXenes. An in-depth molecular dynamics simulation study, combined with experimental kinetic parameters, further revealed that the diffusion of F - in the confined interplanar space is rate-determining for the etching reaction. The expansion of interlayer spacing by polyols effectively reduces the diffusion activation energy of F - and accelerates the etching reaction.

The terahertz (THz) metamaterials integrated with microelectromechanical systems (MEMS) have led to the realization of dynamic control in amplitude, phase, polarization, and spin angular momentum of the THz wave. In this study, we demonstrate an MEMS-based reconfigurable THz metamaterial (RTM) composed of a split ring resonator (SRR) for real-time modulation of THz wave. By gradually increasing the polarization angle of the incident THz wave, the resonant frequency of SRR switches from 0.74 to 1.16 THz, and the maximum modulation depth is more than 70%. When the MEMS-based RTM is actuated by different DC bias voltages, the polarization-dependent transmission intensity and resonant frequency of the device can be actively tuned. MEMS-based RTM shows logical function characteristics that can be used for logic modulators by performing the driving voltages and polarization states as 2-bit input signals and quantizing the transmission response as "on" and "off" states. The logic gates of "NAND" are at 0.439 THz and "AND" is at 0.732 THz. These results offer potential applications for the proposed MEMS-based RTM in tunable and reconfigurable polarization filters, optical switches, programmable logic modulators, and so on.