Abstract:Biofilms establish protective sanctuaries that shield resident bacteria, facilitating resistance. Despite extensive efforts, current chemicals for biofilm eradication remain insufficient, with the reliance on single-structure antimicrobials further exacerbating resistance. Photoisomerizable spiropyran derivatives reversibly transition between conformational states, alternately exerting antimicrobial activity against pathogens and potentially mitigating resistance. However, the biofilm-eradicating potential of spiropyran derivatives remains unverified, while their application is hindered by limited fatigue resistance, suboptimal foliar affinity, and reliance on UV-induced isomerization, all of which are incompatible with sustainable agriculture. Herein, we present a supramolecular strategy to fabricate SpA6(MC)⊂CB[8], a self-assembled complex of the spiropyran derivative SpA6 and cucurbit[8]uril, offering day–night cycle isomerization, enhanced photostability, potent biofilm disruption, improved foliar adhesion, and high antibacterial activity. Notably, neither ambient light nor darkness attenuates its potency, enabling persistent antibacterial activity across diverse molecular configurations. In vivo studies demonstrate its superior dual protective/curative efficacy (54.73%/49.60%) at 200 µg mL−1 against bacterial leaf blight, surpassing thiazole copper (37.63%/33.58%) and bismerthiazol (31.20%/25.59%) without compromising safety, while extended indications reveal its enhanced efficacy (78.99%/63.50%) against citrus canker, outperforming thiazole copper (59.50%/41.42%). This work establishes a paradigm for developing light-responsive supramolecular agrochemicals that combine structural dynamism with enhanced functionality, offering sustainable solutions against plant pathogens.

Abstract:CeO2 was uniformly coated onto the surface of carbon fibers (CF) and the resulting CeO2@CF was employed for the activation of peroxymonosulfate (PMS) to degrade 2,4-Dichlorophenol (2,4-DCP). Under the initial conditions of a PMS concentration of 10 mmol/L, pH range of 3 to 9 and a CeO2@CF mass concentration of 0.1 g/L, the system achieved complete degradation of 50 mg/L of 2,4-DCP with high mineralization efficiency within 60 min. Additionally, the CeO2@CF/PMS system showed high efficiency in the presence of coexisted anions (HCO3−, CO32−, SO42−, Cl−) and exhibited excellent purification capability for actual coking wastewater. Combined with characterization analyses (SEM-EDS, XRD, Raman, XPS, and EPR), degradation experiments and radical quenching experiments, the physicochemical properties of the prepared catalyst and the 2,4-DCP degradation mechanism were explored. Results revealed that CeO2 was uniformly coated on the CF surface, maintaining a regular framework structure. During this process, Ce4+ in CeO2 was reduced to Ce3+, resulting in numerous electron-rich oxygen vacancies forming inside CeO2@CF. Furthermore, the CeO2 coating increased the amount of oxygen-containing groups (C=O) on the surface of CF and graphite defects. In the CeO2@CF/PMS system, •O2− and 1O2 were generated at the active sites of the oxygen vacancies (Vo) and C=O with 1O2 dominated non-free radical pathway and played a notable role in the 2,4-DCP degradation process.

Abstract:Constructed wetlands (CWs) technology has been widely used to treat agricultural non-point source pollution. However, knowledge about the impact mechanism and distribution characteristics of microplastics (MPs) on pesticide treatment in CWs is limited. This study employed atrazine (ATZ), a representative pesticide, as a model contaminant, to systematically investigate the impacts of polyethylene microplastics (PE MPs) on the removal of ATZ and nutrients, as well as the enzyme activity and the distribution of functional genes in vertical subsurface-flow CW microcosm. The results showed that compared to the control group (CK), CWs treated with different concentrations of MPs had no significant difference in the removal of ATZ. Moreover, in the second stage (ATZ=400 μg/L), the average removal efficiency of ATZ by CWs containing MPs was slightly higher than that of the CK group. PE MPs reduced the nitrogen removal efficiency of CWs by 1.57 %-3.03 %, but had no significant effect on TP removal. The concentration distribution of PE MPs in the substrate layer exhibited a decreasing trend from top to bottom, and the interception capacity of CWs gradually decreased with time (from 100 % to 97.4 %); When exposed to PE MPs, the activities of enzymes in substrate related to nitrogen metabolism were inhibited; Moreover, the addition of PE MPs in CWs promoted the removal of ATZ by increasing the abundance of ATZ metabolizing bacteria (Hydrogenophaga, Zoogloea, Rhizobium, etc.) and ATZ degradation key genes (atzA and trzN). These results not only provide theoretical support for the practical application of CWs in the treatment of pesticide wastewater, but also provide a theoretical basis for the environmental risk control of pesticide non-point source pollution ecological treatment technology in the presence of MPs.

Abstract:Lateral flow immunoassays (LFIA) have been acknowledged as the promising on-site screening method for food survey. Monoclonal antibodies against benzo[a]pyrene (BaP) conjugated with enzyme-mimetic probes, a multi mode LIFA strips were systemically constructed and evaluated. The PBNPs@mAbs based LFIA could conduct triple measurement in 14 min. This assay had good limit of detections (LODs of 0.057, 0.035, and 0.106 μg kg−1), ultra calibration ranges (0.23–500, 0.076–56, 0.69–167 μg kg−1), and the recoveries ranging from 86 % to 105 % with the precision less than 12 %. Compared with the reported methods, the LODs were 175-, 285- and 94- folds enhanced, and dynamic linear ranges were greatly expanded. Finally, this novel PBNPs@mAbs LFIA assay with simplicity, rapidity, and sensitivity was successfully utilized for the determination of BaP in vegetable oils, which could be used as a superior enzyme-mimetic on-site analytic platform in food safety.

Abstract:Vanadium-titanium magnetite tailing colloids (TCs) from mineral weathering and industrial production can cause overlooked vanadium groundwater pollution due to their mobility and releasable vanadium. This study investigated the stability and transport mechanisms of vanadium-titanium magnetite TCs under various solution chemistries, including pH, ionic strength (IS), acetic acid (AA), oxalic acid (OA), and citric acid (CA), via field survey, batch, and column experiments with numerical modeling. The results showed field-existing evidence of TCs, AA, OA, and CA in the groundwater of the V-Ti magnetite tailing pond. The edge-face interaction between TCs promoted TCs aggregation around the isoelectric point. AA promoted, while OA and CA inhibited TCs aggregation under all pH and IS. Stronger aggregation was induced by the increased concentration of AA, but contrary to OA and CA. The critical coagulation concentration (CCC) of TCs changed from 34.83 mM to 2.04, 424.54, and 561.17 mM after adding 10 mM AA, OA, and CA at pH 7. As the concentration of LMWOAs increased, stronger aggregation was induced. Increasing solution pH and decreasing IS promoted TCs transport. The ripening phenomenon occurred in the BTCs when IS exceeded 30 mM. AA inhibited TCs transport under acidic and neutral conditions by forming AA-TC-quartz sand ternary complexes, while OA and CA promoted transport at all pH. The variation of acid concentration showed insignificant effects on the TCs transport. DLVO and XDLVO interactions highly regulate TCs stability and transport, and the Langmuirian blocking and ripening featured retention profiles of TCs can be well described using the modified reactive transport model, the Langmuirian kinetic equation and the ripening kinetic model. This research is the first systematic study of vanadium-titanium magnetite TCs behaviors under different solution chemical conditions, and provided a novel strategy for groundwater pollution prevention of TCs by considering plants capable of secreting AA.

Abstract:Efficacious chemotherapy and real-time therapeutic monitoring remain major challenges in cancer treatment. Traditional systems often lack tumor specificity, limiting efficacy, and hindering therapy optimization. Moreover, the absence of real-time monitoring can lead to missed opportunities and increased risks of side effects. Herein, we designed a self-reporting ratiometric AIEgen-peptide nanoprobe (TPE-1(Hyd-DOX)-DEVD) for activatable chemotherapy and noninvasive imaging of therapeutic outcomes. When doxorubicin (DOX) in the nanoprobe is selectively activated in the acidic tumor microenvironment, the ensuing caspase-3 cascade triggers a morphological transformation of the nanoprobe that amplifies the TPE fluorescence. This enhancement allows the TPE/DOX fluorescence ratio to serve as an indicator for monitoring DOX activation and for providing therapeutic feedback. Both in vitro and in vivo studies demonstrated that TPE-1(Hyd-DOX)-DEVD exhibited an impressive tumor suppression efficacy and excellent biocompatibility. This study highlights the strong potential of this nanoprobe as a valuable tool for cancer theranostics, offering hope for more effective and personalized treatment strategies.

Abstract:Mining operations metallic sulfur minerals expose to oxidizing conditions, resulting in the production of acidic mine drainage (AMD). This work investigates how the inclusion of aluminous clay (AC) influences the speciation changes of sulfur (S), iron (Fe), aluminum (Al), and silicon (Si) on the surface of pyrite while it undergoes the bio-oxidative dissolution process. The results show that adding a small amount of AC (≤4.0 g/L) promotes the bio-oxidation of pyrite. Conversely, the addition of a larger amount of AC (>4.0 g/L) inhibits the oxidation of pyrite. The oxidation process of pyrite conforms to the "polysulfide-thiosulfate" complex oxidation pathway. The breakdown of AC involves the consumption of H+ ions and the release of Al3+ ions. This process contributes to changes in hydrochemical composition, facilitating the hydrolysis of Fe3+ and Al3+ to create a secondary mineral layer on the pyrite's surface. This in turn, encourages the formation of FeSn or Fe1-xS. These findings suggest the potential to control the oxidative dissolution of pyrite by regulating the formation of a solid film passivation layer. This work gives a new insight into devising strategies aimed at remediation and treatment, presenting avenues to mitigate environmental pollution caused by AMD.

Abstract:In order to elucidate the dynamic changes of quality characteristics in Xanthoceras sorbifolium leaf tea (XLT), this work investigated the chemical components, volatile profile, and antioxidant properties at key stages of fixation, shaping, and drying. The process of fixation and drying emerged as critical stages that affected the chemical components and taste of XLT. Total polyphenols, reducing sugars and chlorophyll were the differential compounds, which decreased by 29.1 %, 63.3 % and 69.5 % during processing, respectively. Threonine, glycine, arginine, reducing sugar, caffeine, catechin (C), and epicatechin gallate (ECG) were primary taste characteristic compounds. A total of 95 volatile organic components (VOCs) and 24 key odorants with relative odor activity value (ROAV) > 1.0 were identified in XLT, ethyl 2-methylbutanoate-D, dimethyl disulfide, and ethyl isobutyrate (ROAV = 100) were the central contributors to volatiles profile. Moreover, tea manufacturing enhanced the antioxidant potency composite (APC) by 1.1 %, primarily due to its high water extract content.

Abstract:Cinnamon essential oil has gained widespread attention in the food industry as a safe and effective preservative. However, its low water solubility and high volatility limit its application in food, making the use of natural emulsifiers for its emulsification an increasingly popular focus of research. This study focuses on the extraction of galactomannan-rich aqueous extracts from Gleditsia sinensis seeds using a low-energy, low-pollution microwave-assisted method. The extracted aqueous extracts from Gleditsia sinensis seeds was combined with soy protein isolate to prepare a cinnamon essential oil emulsion, followed by physicochemical characterization and stabilization mechanism studies. The emulsions demonstrated excellent storage stability at 4 °C, along with robust ionic, pH, temperature, and freeze-thaw stability. Furthermore, the emulsions exhibited significant antioxidant activity and effectively inhibited the growth of Staphylococcus aureus and Listeria monocytogenes, highlighting their potential for application in food preservation. Preservation trials with orange juice confirmed that our emulsion achieved preservation comparable to that of the commercial food preservative potassium sorbate. These findings provide valuable insights for developing stable and functional natural food emulsifiers.

Abstract:The dense extracellular matrix (ECM) and immunosuppressive tumor microenvironment represent two major challenges in the treatment of triple-negative breast cancer (TNBC). To address these obstacles, this study has developed a polymer micelle (NTP) for ECM remodeling and mitigation the immune microenvironment, based on activating endogenous matrix metalloproteinases (MMP) and suppression indoleamine 2,3-dioxygenase (IDO). Through self-assembly technology, this micelle effectively incorporates chemotherapy drugs (camptothecin (CPT) and cinnamaldehyde (CA)), reactive oxygen species (ROS) stimulants, nitric oxide (NO) donor and IDO inhibitor (NLG919), where CPT and CA have been reported to help generating ROS mainly in the mitochondrion. The guanidine group of poly-L-arginine (PArg), as an NO donor, can react with ROS to generate NO. The micelles aim to achieve significant therapeutic outcomes through robust drug penetration and anti-tumor immunity in multimodal therapy. They exhibit remarkable tumor tissue penetration ability, facilitating precise targeting of mitochondria and ROS production stimulation. Building upon this therapeutic foundation, the micellar system achieves in situ NO release, which effectively degrades the ECM through the activation of MMPs, while simultaneously promoting tumor cells apoptosis. Furthermore, the encapsulated NLG919 can be released and effectively mitigating the immunosuppressive milieu and triggering anti-tumor immune responses. Experimental results demonstrate that the micelles exhibit significant anti-tumor effects both in vitro and in vivo, accompanied by favorable biocompatibility. This study provides new insights into the application of subcellular targeting drug delivery systems in TNBC treatment, potentially heralding a new breakthrough in TNBC therapy.

Abstract:Smart drug delivery systems that activate in response to tumor-specific signals and include real-time monitoring are highly desirable in personalized cancer treatment. Herein, a new chimeric peptide, PpIX-1-DG, is designed with an integrated "gear set" mechanism for achieving auto-activation, cascade-amplification and self-reporting features in precision photodynamic therapy. The peptide, comprised of a photosensitizer and a gemcitabine prodrug, self-assembles into nanoparticles in physiological condition. Upon cellular uptake, nanoparticles specifically respond to elevated GSH levels in cancer cells to release gemcitabine, thereby exerting its chemotherapeutic effect for initiating apoptosis and activating caspase-3—the first "auto-activation" gear. Next, caspase-3 catalyzes the production of photosensitive PpIX-1, resulting in elevation of intracellular ROS in A549 cells, thereby inducing mitochondrial dysfunction and more apoptosis upon photoirradiation. This process elevates caspase-3 levels and activates additional photosensitizers, marking the second "cascade amplification" gear. Intravenous administration of PpIX-1-DG alongside photoirradiation shows enhanced antitumor efficacy and minimal systemic toxicity. Notably, the fluorescence of PpIX-1-DG activated by caspase-3 facilitates real-time monitoring, enabling the third "self-reporting" gear for therapeutic outcome tracking in vitro and in vivo. Together, this "three-in-one" strategy enables precision photodynamic therapy and synchronous therapeutic monitoring, holding great potential in the realm of cancer nanomedicine.

Abstract:TLR2 agonists represent promising cancer immunotherapeutic due to their unique combination of potency and safety. SMU-C68, a human TLR1/2 specific small molecule agonist was identified, exhibiting a remarkable four-fold increase in biological activity compared to previously reported SMU-C80 with enhanced aqueous solubility. The cellular and protein level results confirmed that SMU-C68 facilitated the dimerization of TLR1 and TLR2 proteins, leading to the specific activation of TLR1/2 heterodimers. Upon activation, TLR2 recruited the adaptor protein MyD88, initiating downstream NF-κB signaling pathway. Moreover, treatment with SMU-C68 induced the release of pro-inflammatory factors, such as TNF-α and IL-1β, in human PBMC cells. Notably, SMU-C68 exhibited good selectivity towards human species and showed minimal effects on murine cells. Furthermore, in vitro co-culture experiments demonstrated that SMU-C68 exerted a positive influence on immune cell activation and tumor cell apoptosis. These findings strongly emphasize the potential of SMU-C68 in modulating immune responses and eliciting anti-tumor activity.

Abstract:Tyrosine kinase 2 (TYK2), a critical scaffolding kinase required for type I interferon, IL-12 and IL-23 cytokine signaling, represents a compelling therapeutic target for various autoimmune diseases. However, existing TYK2 inhibitors only modulate its kinase activity. Here, we report the development of a first series of CRBN-recruiting TYK2 PROTACs based on an allosteric TYK2 inhibitor. Optimization of the potency and metabolic stability identified 15t as an exceptionally potent and selective TYK2 degrader with a DC50 value of 0.42 nM and a Dmax value of 95%, which potently and selectively blocked TYK2-dependent signaling. Importantly, 15t was active in vivo and significantly suppressed TYK2-mediated pathology in a murine psoriasis model without apparent toxicity. Collectively, our study provides a potentially valuable chemical knockdown probe for subtype-selective TYK2 degradation and further understanding TYK2 scaffolding biology, demonstrating the therapeutic potential of TYK2 PROTACs in immuno-inflammatory diseases such as psoriasis.

Abstract:The migration behavior of pesticides in water under the coexistence of microplastics is not sufficiently known. In this study, the effects of main environmental factors on the adsorption characteristics of atrazine (ATZ) and imidacloprid (IMD) on aged polyethylene (PE) microplastics in aqueous solution were investigated, and the adsorption mechanisms were also discussed. The results showed that the pseudo-first-order and Freundlich models fitted the adsorption kinetics and isotherms of ATZ and IMD on PE well. The adsorption capacity of PE toward ATZ and IMD could be reached to as high as 350.40 μg/g and 327.75 μg/g, respectively, at 298 K and pH 7. Moreover, the adsorption process of the two pesticides was a spontaneous and endothermic process. The removal amount of ATZ by PE was highest at pH= 3, and the removal rate decreased with the increasing of pH; while the removal rate of IMD by PE was best under neutral conditions. The increase in HA concentration reduced the adsorption capacity of ATZ (4.79–57.2 %) and IMD (3.94–30.02 %). Besides, the main adsorption mechanism of ATZ and IMD was hydrophobic interaction. This study provides a theoretical reference for investigating the effects of aging microplastics on the migration behavior of different pesticides in water environments.

Abstract:The non-destructive deburring and hydrophilic surface machining of 3D printed Polyetheretherketone (PEEK) implants surface is critical for post-processing production of the implants. A green sodium bicarbonate abrasive jet machining technology was proposed in this study, aiming to ensure low damage of implants surface while effectively deburring and creating a hydrophilic surface conducive to cell adhesion. By comparing the machining effects of sodium bicarbonate abrasive and other hard abrasives (alumina and glass bead) under various jet pressures and angles, it was confirmed that sodium bicarbonate abrasive jet machining technology could provide the low damage (Ra = 1.75∼3.73 μm), moderate machining rate (0.24∼2.26 mg/s), excellent deburring performance, and outstanding surface cleanliness. Based on the comparison of experimental data and finite element simulation results, the fluid characteristics of abrasive particle beam and the combined machining mechanism (compression and plowing effect) of sodium bicarbonate abrasive jet machining technology were determined. Based on the consistent crystal phase and high purity displayed in the characterization of recycled abrasives, the feasibility of the designed abrasive recycling procedure was confirmed. Moreover, the fluorescence staining results of the adherent cell proliferation experiments confirmed that the sodium bicarbonate abrasive jet machining technology could effectively promote cell adhesion and growth by providing the matte elongated scratch-like micro-texture for the PEEK implants surface. In the future, this technology could facilitate the development for post-processing treatments in 3D printed PEEK implants additive manufacturing process.