Covalent organic frameworks (COFs) rely on a large number of nitrogen or nitrogen-sulfur atoms as active sites for optimal adsorption, but this can have undesirable outcomes. In this study, three phenol-modified covalent organic frameworks (PCOF-x, x = 1-3) with a low number of N atoms were synthesized, featuring strong structural protonation and reduction capabilities. The maximum adsorption capacities of PCOF-1, PCOF-2 and PCOF-3 for Au3+ ions at room temperature were 4787, 4240 and 2850 mg/g, respectively. These results demonstrate that COFs can achieve exceptionally high adsorption levels without the need for extensive nitrogen modification. All the three COFs exhibit exceptional thermal stability and regenerative properties, maintaining high selectivity and adsorption efficiency even in the practical electronic waste water. These COFs can convert 90% of Au3+ into Au0, which is highly significant for gold recovery and conversion. Our research has proven that low-nitrogen COFs can be explored to achieve exceptionally high adsorption capacities by reducing the side reactions.

The photocatalytic degradation efficiency of BiVO4 is limited by the easy recombination of photogenerated electron-hole (e--h+) pairs. Hence, this study first prepared BiVO4/SiO2 piezo-photocatalyst with core-shell structure to enhance piezo-photoelectrochemical (Piezo-PEC) water splitting activity and piezo-photocatalytic (PPC) degradation performance of tetracycline (TC), rhodamine B (RhB) and methylene blue (MB). Under the synergistic excitation of illumination and 40 kHz ultrasound, the BiVO4/SiO2-C2 photoelectrode shows the highest photocurrent density of 0.517 mA/cm2 at 1.23 V vs. RHE, which is 2.88 times higher than pure BiVO4-H. The enhanced Piezo-PEC water splitting activity is attributed to the SiO2 shell expanding the light absorption range and promoting carrier migration through interface band engineering. Additionally, X-ray photoelectron spectroscopy confirms that SiO2 can induce more complex asymmetric structures of V in BiVO4, thereby enhancing the piezoelectric effect and inhibiting the carrier recombination. BiVO4/SiO2-C2 shows fascinating PPC degradation performance of TC (91.3 %), RhB (95.2 %) and MB (94.1 %) within 40 min, respectively. Meanwhile, BiVO4/SiO2-C2 exhibits a PPC degradation rate of over 80 % after 5 cycles, indicating the SiO2 coating effectively reduces the photocorrosion rate of BiVO4 and improves stability. Free radical capture experiments further confirmed that h+ and hydroxyl radical (center dot OH) serve as the main reactive species in PPC degradation, while e- and superoxide radical (center dot O2-) serve minor roles. This finding may inspire the construction of a dual-functional piezo-electrocatalyst to enhance Piezo-PEC and PPC degradation activity through the synergistic effect of high carrier separation efficiency and stability.

Terrestrial ecosystems heavily depend on vegetation,which responds to carbon dioxide （CO 2 ） fertilization in hot and humid regions.The subtropical humid karst region is a hot and humid region;whether and to what extent CO 2 fertilization affects vegetation changes in such regions remains unclear.In this study,we investigated the degree to which CO 2 fertilization influences vegetation changes,along with their spatial and temporal differences,in the subtropical humid karst region using time-lag effect analysis,a random forest model,and multiple regression analysis.Results showed that CO 2 fertilization plays an important role in vegetation changes,exhibiting clear spatial variations across different geomorphological zones,with its degree of influence ranging mainly between 11%and 25%.The highest contribution of CO 2 fertilization was observed in the karst basin and non-karstic region,whereas the lowest contribution was found in the karst plateau region.Previous studies have primarily attributed vegetation changes in subtropical humid karst region to ecological engineering,leading to an overestimation of its contribution to these changes.The findings of this study enhance the understanding of the mechanism of vegetation changes in humid karst region and provide theoretical and practical insights for ecological and environmental protection in these regions.

Pathogenic infections pose a major global health risk due to their high morbidity and mortality. Rapid and accurate bacterial discrimination is currently an emerging trend in the fields of food safety, medical diagnostics, and environmental monitoring. This study introduces a comprehensive platform for the rapid and broadspectrum identification of pathogenic bacteria, integrating bacteria enrichment and online lysis, nanoelectrospray ionization (nanoESI), miniature mass spectrometry (MS) analysis, and machine learning algorithms. Capture efficiencies exceeding 95 % for various bacterial species were achieved through interactions between polyethyleneimine-functionalized magnetic nanoparticles (PEI-MNPs) and bacteria following a 10-minute incubation period. Subsequently, the bacteria similar to MNPs complexes were subjected to online lysis via a simple ultrasound-assisted electrospray solvent cracking process to release bacterial extracts. Using nanoESI and miniature MS analysis, fingerprints providing comprehensive characterization of bacterial signature information were obtained rapidly. By employing a kNN machine learning model, the platform successfully identified different bacteria species and E. coli strains with 100 % overall identification accuracy within 15 minutes. Meanwhile, E. coli and S. aureus served as model bacteria for the quantitative evaluation of the platform, which could successfully distinguish concentrations of E. coli and S. aureus at 10(4) and 10(5) cfu/mL, respectively, and their mixture samples at 10(6) cfu/mL. Its practicality was further validated through the accurate identification of bacteria in real samples, demonstrating promising potential for real-time bacterial contamination monitoring in on-site environments.

This study investigated the effects of three fertilizer components-urea [CO(NH2)2], calcium phosphate [Ca3(PO4)2], and sodium sulfate [Na2SO4]-as well as their combinations, on the migration behavior of polyethylene terephthalate (PET) nanoplastics in quartz sand porous media, using laboratory column experiments and molecular dynamics simulations.Experimental results showed that under single-fertilizer conditions, all three components significantly inhibited the migration of PET nanoplastics. Under the same experimental conditions, the order of inhibitory effect was Ca3(PO4)2>Na2SO4> CO(NH2)2. Among them, Ca3(PO4)2 exhibited the most pronounced inhibitory effect through the dual mechanisms of reducing electrostatic repulsion and facilitating Ca2+ bridging. Additionally, a synergistic effect was observed between mixed fertilizer components, which further enhanced the inhibitory effect on PET migration. Results from molecular dynamics simulations demonstrated that the individual addition of each of the three fertilizer components altered the interaction energy between the PET nanoplastic suspension and the quartz sand surface. This study reveals the inhibitory mechanism by which fertilizers influence PET nanoplastics in porous media: fertilizers modify the surface properties of the medium and the stability of PET nanoparticles, thereby inhibiting PET migration. The findings provide an important theoretical basis for the prevention and control of microplastic pollution in agricultural practices, soil, and groundwater.

Emerging contaminants such as plastics and pharmaceuticals pose significant challenges to the environmental fate and transport processes in soil and groundwater systems. This study investigates the co-transport behavior of polyethylene terephthalate (PET) nanoplastics and Ibuprofen (IBP) in porous media through column experiments and molecular dynamics (MD) simulations, examining the key factors affecting their migration. The experimental results showed that IBP significantly inhibited the migration of PET in quartz sand, and the inhibitory effect was enhanced with the increase of IBP concentration; high flow rates both promoted the migration of PET and IBP in porous media. In addition, high ionic strength inhibited PET migration in porous media, and the addition of IBP enhanced PET migration to some extent under the same conditions. This was similarly found in the co-transport system under HA conditions. MD simulations reveal stronger interaction forces and greater binding stability between PET and quartz sand compared to IBP and quartz sand. Furthermore, a two-site kinetic deposition model was employed to simulate the retention and transport of PET nanoplastics and IBP in porous media, achieving excellent agreement with the experimental results. These findings enhance the understanding of the environmental fate and risks associated with microplastics in subsurface soil and water systems and provide a scientific basis for developing advanced contaminant mitigation strategies.

Perfluorooctane sulfonate (PFOS) is a persistent environmental contaminant with adverse effects. Alongside PFOS, its substitutes, such as 6:2 chlorinated polyfluorinated ether sulfonate (F-53B) and 6:2 fluorotelomer sulfonic acid (6:2 FTSA), are frequently detected in aquatic environments. While the effects of PFOS and its substitutes on the aquatic organism behavior have been observed, the underlying mechanisms of these effects remain poorly understood. In this study, an online biological monitoring system was utilized to investigate the behavioral effects of 7-day exposure to PFOS, F-53B, and 6:2 FTSA in adult zebrafish (Danio rerio), and assess alterations in neurotoxicity-related biomarker levels. Results demonstrate that exposure to PFOS, F-53B, and 6:2 FTSA significantly reduced the behavioral strength (BS) and the amplitude of circadian rhythm in zebrafish. Notably, PFOS and 6:2 FTSA exposure induced circadian rhythm phase shifts. Furthermore, acetylcholinesterase (AChE) activity and dopamine (DA)/melatonin (MT) levels showed significant reductions consistent with BS alterations across all exposure groups. Molecular docking analysis revealed that PFOS, F-53B, and 6:2 FTSA exhibited significant binding affinities to related receptors. Among the three pollutants, F-53B exerted the most pronounced effects on BS values, circadian rhythm amplitude, and levels of related biomarkers. In contrast, 6:2 FTSA displayed the most significant impact on circadian rhythm phase shifts. These findings suggest that the effects and the underlying mechanisms of PFOS and its substitutes on zebrafish behavior may vary. A comprehensive evaluation of the neurotoxicity of PFOS substitutes for aquatic organisms is required to prevent underestimation of their potential risks.

The drainage of pore water, particularly bound water, plays an important role in determining the mechanical and engineering properties of clay. This study focuses on the effects of bound water on compressibility and drainage in saturated clayey silt and silty clay during consolidation utilizing low-field nuclear magnetic resonance (LFNMR). The results show that the water content decreases with increasing stress, accompanied by a decreasing proportion of free water and an increasing proportion of weakly bound water in the soil. The proportion of strongly bound water remains relatively constant, demonstrating its non-participation in the drainage process. The drainage during consolidation was divided into two stages: (I) the drainage of free water alone and (II) the simultaneous drainage of weakly bound water and free water when the stress exceeds the critical stress related to clay content. A drainage mechanism considering bound water is revealed by a modified drainage function. The modified drainage function, considering the immobile strongly bound water, solves the problem of underestimating the drainage mass in comparison with the classic drainage function. The results also show that a high clay content improves consolidation and drainage and facilitates the release of weakly bound water. This study provides an innovative scheme to quantify the dynamic evolution of different pore water types and the drainage mechanism influenced by the properties of the bound water during consolidation, and offers a new insight into the prediction of consolidation settlement.

In this study, four types of Fe3O4-based magnetic nanospheres were functionalized with distinct surface groups to examine how surface chemistry influences their co-transport with tetracycline (TC) in porous media. The functional groups investigated are carboxyl (−COOH), epoxy (−EPOXY), silanol (−SiOH), and amino (−NH2). Particles bearing −COOH, −EPOXY, or −SiOH are negatively charged, facilitating their transport through porous media, whereas −NH2-modified particles acquire a positive charge, leading to strong electrostatic attraction to the negatively charged TC and quartz sand, and consequently substantial retention with reduced mobility. Adsorption of TC onto Fe3O4-MNPs is predominantly chemisorptive, driven by ligand exchange and the formation of coordination complexes between the ionizable carboxyl and amino groups of TC and the surface hydroxyls of Fe3O4-MNPs. Additional contributions arise from electrostatic interactions, hydrogen bonding, hydrophobic effects, and cation–π interactions. Moreover, the carboxylate moiety of TC can coordinate to surface Fe centers via its oxygen atoms. Molecular dynamics simulations reveal a hierarchy of adsorption energies for TC on the differently modified surfaces: Fe3O4-NH2 > Fe3O4-EPOXY > Fe3O4-COOH > Fe3O4-SiOH, consistent with experimental findings. The results underscore that tailoring the surface properties of engineered nanoparticles substantially modulates their environmental fate and interactions, offering insights into the potential ecological risks associated with these nanomaterials.

The incorporation of water in high-pressure minerals is essential for the water cycle within the interiors of terrestrial planets. Majoritic garnet, a major component in the mantles of Earth and Mars, plays a significant role in this context. In this study, we use first-principles simulations to explore water incorporation mechanisms in MgSiO3-majorite, which is a key end-member of majoritic garnet, at conditions up to 2,000 K and 20 GPa. By dealing with the relationship between chemical potential and the Gibbs free energy changes for the reactions at equilibrium conditions, we determine the ratios of the seven potential hydrous defects. Our results reveal that the Si2 and Si3 defects, which are of the hydrogarnet-type, dominate water incorporation in MgSiO3-majorite. In addition, we evaluate the effects of these hydrous defects on seismic wave velocities. The presence of Si2 and Si3 defects, with an expected water concentration of similar to 700 ppm, has a small effect on both P-wave and S-wave velocities. Nevertheless, the influence of water on lateral variations in the seismic wave velocities of MgSiO3-majorite, which is opposite to that found for ringwoodite, offers a potential tool for investigating compositional heterogeneities in hydrated regions of planetary mantles.

A key issue about radioactive waste disposal and nuclear accident contamination control is the retention of radionuclides in clay minerals. The cation (Cs+, Rb+, Na+, K+) selectivity in montmorillonite (Mt) interlayers have not been quantitatively studied. This work employs classical molecular dynamics (CMD) to systematically investigate the interlayer structure, swelling properties, diffusion dynamics, and cation exchange processes. The selectivity of alkali ions within the interlayer space coupled with clay swelling/collapse under different water activity (aw) and cation activity, has been quantified. Both Cs-, Rb-Mt demonstrate a monolayer hydrate configuration as the most stable state. The mobility of intercalated species, as indicated by self-diffusion coefficients, exhibits a stepwise trend with increasing water content. The cationic selectivity within the interlayer follows the order Cs+ > Rb+ > K+ > Na+ at aw = 1.0. The logarithm values of the selectivity coefficients for Cs/Rb relative to Na/K are as follows: logKc(Cs/K) = 0.73, logKc(Cs/Na) = 1.62, logKc(Rb/K) = 0.62, and logKc(Rb/Na) = 1.57 at aw = 1.0. A model correlating selectivity coefficients with water activity has been proposed. It is noted that Cs+ and Rb+ ions tend to accumulate within the interlayer as water activity decreases, and interlayer Rb+ competes with Cs+ for exchange positions at low water activity. These results can be used to quantify cationic partitioning during the remediation of radiocesium contamination in soil and weathering processes of sediments.

Oriented attachment (OA), that is, the coalescence of crystals through attachment on coaligned crystal faces, is a nonclassical crystal growth process. Before attachment, a mesocrystal consisting of coaligned parallel crystals but with liquid separating them was observed. Fundamental questions such as why OA is kinetically favored and whether a mesocrystal stage is a prerequisite for OA are raised. Through combining brute-force molecular dynamics simulations and path samplings based on extensive umbrella simulations, we address these questions with a case study on the OA of a mica nanocrystal onto a mica crystal substrate in water. Brute-force simulations show that if two mica crystals are attached but largely misaligned, coalignment hardly appears. Thus, if OA is possible, then coalignment must appear before the attachment between crystals. Electrophoresis of the nanocrystal toward the substrate surface is spontaneous, but mesocrystal formation is occasional, also shown by brute-force simulations. Free energies along different pathways show that OA is spontaneous and kinetically favored over non-OA, and a mesocrystal formation is just a bifurcation in the pathway. OA is through a pathway in which the nanocrystal is tilted with respect to the substrate. Part of the nanocrystal is attached to the substrate first, and then, OA is gradually completed. Once a mesocrystal is occasionally formed, then a jump event is needed for the nanocrystal to get back to the OA pathway. The sampling technique here can hopefully guide the design of nanostructured materials facilitated by OA.

Targeting XPO1 inhibition has emerged as a promising therapeutic strategy in cancer treatment. Despite the numerous XPO1 inhibitors reported to date, no XPO1 degraders have been disclosed. In this study, we reported the design, synthesis and biological characterization of small-molecule XPO1 degraders based upon the proteolysis targeting chimera (PROTAC), marking the first public disclosure of XPO1 degraders. The potent PROTAC compound 2c was identified, demonstrating effective degradation of XPO1 protein in MV4-11 acute myeloid leukemia (AML) cells, with a DC50 of 23.67 nM. Treatment with 2c resulted in significant antiproliferative effects, with IC50 values of 0.142 ± 0.029 μM in MV4-11 cells and 0.186 ± 0.024 μM in MOLM-13 cells. Additionally, 2c induced apoptosis, inhibited NF-κB activity, and caused G1 phase cell cycle arrest. The study highlights the therapeutic potential of targeting XPO1 degradation in AML treatment and emphasizes the advantages of PROTAC technology in developing novel anticancer strategies. These findings provide a foundation for further exploration of XPO1 degraders in cancer therapy, offering new hope for effective treatment options in hematological malignancies.

Nanoplastics (NPs) are released into surface water due to the widespread use of plastics, undergoing aging from environmental and human factors that alter their physical and chemical characteristics. However, detecting NPs remains challenging, resulting in limited research on their behavior in surface water and their removal efficiency by drinking water treatment. This study utilizes palladium-doped polystyrene nanoplastics (PSNPs) as tracers to enable precise detection and quantification through ICP-MS, thereby overcoming the limitations of conventional detection methods. PSNPs are aged using solar irradiation and ozone to simulate both natural and artificial aging processes, affecting the physical and chemical properties of NPs, which in turn influence their behavior in water treatment systems. Moreover, the study investigates the impact of various coagulation conditions, including different coagulants (AlCl3 and PACl), pH levels (4-9), and humic acid (HA) concentrations (0-10 mg/L), on the of both aged and nonaged NPs. The results demonstrate solar aging triggers significant morphological changes in PSNPs, while ozone aging induces more oxygen functional groups on PSNPs (CIozone=20.99; CIsolar=0.70), increasing sensitivity to HA concentrations and resulting in reduced removal efficiencies for ozone aged PSNPs by AlCl3 (68.68 %) and PACl (74.74 %). In addition, PACl achieves higher PSNPs removal efficiencies (REmin=88.59 %) than that of AlCl3 (REmin=85.57 %) under varied pH levels. This research fills a gap in understanding aged NPs behavior in surface water and offers practical solutions for optimizing coagulation for NPs removal, enhancing our ability to predict NPs environmental fate and manage NPs pollution to ensure drinking water safety.

Rapid and accurate on-site detection of chemical warfare agents (CWAs) could defend military and civilian populations against current and emerging chemical weapons. With the development of ambient ionization and linear ion trap technology, the rapid and accurate quantitative determination method of CWAs based on direct ionization and multistage mass spectrometry has attracted widespread attention. In this study, a microliter electrospray ionization-miniature linear ion trap mass spectrometry (LIT-MS) instrument was designed and constructed, and the effects of quadrupole enhanced dipole resonance excitation on the resolution and sensitivity were investigated; consequently, the parameters of CWAs detection were optimized. Based on the broad time-frequency ion excitation technology, accurate multiple reaction monitoring (MRM) quantitative analysis of DMMP (G-series agent simulants, m/z 125 → m/z 93) was obtained. The linear correlation coefficient in the concentration range of 1 to 20 μg/mL could reach 99.02%, and the relative standard deviations (RSD) of continuous repeatability, interday repeatability, and intraday repeatability were all less than 10%. The results showed that the accurate pseudo-MRM detection method based on miniature linear ion trap mass spectrometry for CWAs detection was feasible.

Abrin toxin, highly dangerous with an estimated human lethal dose of 0.1-1 mu g per kg body weight, has attracted much attention regarding criminal and terroristic misuse over the past decade. Therefore, developing a rapid detection method for abrin toxin is of great significance in the field of biosecurity. In this study, based on the specific dissociation method of an immobilized enzyme reactor, the trypsin immobilized reactor Fe3O4@CTS-GA-Try was prepared to replace free trypsin, and the immobilized enzyme digestion process was systematically investigated and optimized by using bovine serum albumin as the simulant of abrin. After 5 min one-step denaturation and reduction, a satisfactory peptide number and coverage were yielded with only 15 s assisted by an ultrasound probe to identify model proteins. Subsequently, abrin was rapidly digested using the established method, resulting in a stable and highly reproducible characteristic peptide number of 39, which can be analyzed by nanoelectrospray ionization coupled with high-resolution mass spectrometry. With the acquisition mode of full MS scan coupled with PRM, not only MS spectroscopy of total abrin peptides but also the corresponding MS/MS spectroscopy of specific abrin peptides can achieve the characteristic detection of abrin toxin and its different isoforms in less than 10 minutes, with high repeatability. This assay provides a universal platform and has great potential for the development of on-site detection and rapid mass spectrometric analysis techniques for macromolecular protein toxins and can further be applied to the integrated detection of chemical and biological agents. A method combining ultrasound probe-assisted digestion with immobilized enzyme reactors and direct nanoelectrospray ionization-high-resolution mass spectrometry was developed for rapid abrin toxin analysis.

In order to address the issues of energy depletion, more resources are being searched for in the deep sea. Therefore, research into how the deep-sea environment affects cement-based materials for underwater infrastructure is required. This paper examines the impact of ocean depth (0, 500, 1000, and 1500 m) on the ion interaction processes in concrete nanopores using molecular dynamics simulations. At the portlandite interface, the local structural and kinetic characteristics of ions and water molecules are examined. The findings show that the portlandite surface hydrophilicity is unaffected by increasing depth. The density profile and coordination number of ions alter as depth increases, and the diffusion speed noticeably decreases. The main cause of the ions’ reduced diffusion velocity is expected to be the low temperature. This work offers a thorough understanding of the cement hydration products’ microstructure in deep sea, which may help explain why cement-based underwater infrastructure deteriorates over time.

Cefiderocol is the first approved catechol-conjugated cephalosporin against multidrug-resistant Gram-negative bacteria, while its application was limited by poor chemical stability associated with the pyrrolidinium linker, moderate potency against Klebsiella pneumoniae and Acinetobacter baumannii, intricate procedures for salt preparation, and potential hypersensitivity. To address these issues, a series of novel catechol-conjugated derivatives were designed, synthesized, and evaluated. Extensive structure-activity relationships and structure-metabolism relationships (SMR) were conducted, leading to the discovery of a promising compound 86b (Code no. YFJ-36) with a new thioether linker. 86b exhibited superior and broad-spectrum in vitro antibacterial activity, especially against A. baumannii and K. pneumoniae, compared with cefiderocol. Potent in vivo efficacy was observed in a murine systemic infection model. Furthermore, the physicochemical stability of 86b in fluid medium at pH 6-8 was enhanced. 86b also reduced potential the risk of allergy owing to the quaternary ammonium linker. The improved properties of 86b supported its further research and development.

With the application of engineered nanomaterials and antibiotics in the fields of medicine, aerospace, new energy and agriculture, the associated contamination is detected widely in soil -groundwater systems. It is of great scientific and practical significance to deeply explore the environmental interface process between nanoparticles and antibiotics for the scientific assessment of environmental fate and ecological environmental risks, as well as the development of new composite pollution control technologies. In this study, the co -transport behaviors of positively charged titanium dioxide nanoparticles (TiO 2 -NPs) and negatively charged levofloxacin (LEV) in quartz sand (QS) are investigated in this study. The results show that TiO 2 -NPs hardly flow out when transported alone in the column because of its positive charge, which creates a strong attraction with the negatively charged quartz sand on the surface. When TiO 2 -NPs co -migrate with LEV in porous media, the presence of LEV promotes the transport of TiO 2 -NPs, while the presence of TiO 2 -NPs inhibits LEV transport. Non-XDLVO interactions based on molecular dynamics (MD) simulations can help explain the observed promotion and inhibition phenomena as well as the correlation between TiO 2 -NPs and LEV. The results indicate that TiO 2 -LEV complexes or aggregates can be formed during the co -transportation process of TiO 2 -NPs and LEV in porous media. As flow velocity increases from 0.204 cm min - 1 to 1.630 cm min - 1 , both the transport capacities of TiO 2 -NPs and LEV are enhanced significantly. Under the condition of high citric acid (CA) concentration (15 mmol L - 1 ), the transport capacity of TiO 2 -NPs is slightly inhibited, while the transport capacity of LEV is enhanced. This study provides new insights into the transport of nanometallic oxides and antibiotics in porous media, which suggests that non-XDLVO interactions should be considered together when assessing the environmental risks and fate of nanometallic oxides and antibiotics in soil -groundwater systems.