The continued evolution of influenza viruses can reduce vaccine effectiveness and promote resistance to direct-acting antivirals. ST6GAL1 is required for the formation of α2,6-linked sialylated glycans on respiratory epithelial cells, which serve as major attachment structures for human-adapted influenza A viruses. Here, we prepared a chemically modified siSt6gal1 conjugated with A20FMDV2 and delivered it to the lung by nebulization. The conjugate resisted enzymatic degradation and maintained pulmonary St6gal1 silencing for at least 14 days after a single dose. Following viral challenge, the A20FMDV2-conjugated siSt6gal1 delayed the accumulation of viral nucleoprotein RNA and protein in the lung and reduced neuraminidase activity, infectious viral titers, and inflammatory markers. No obvious acute histopathological, serum biochemical, or hematological abnormalities were detected after a single nebulized dose. Local and sustained silencing of a host susceptibility factor may therefore provide a pre-exposure approach to limiting early influenza A virus replication.
The commercialization of iron-chromium flow batteries (ICFBs) is hindered by sluggish Cr3+/Cr2+ kinetics caused by Jahn-Teller and parasitic hydrogen evolution reaction (HER). In this work we propose a collaborative “dual-regulation” strategy leveraging the synergistic effects of -OH hydrophilicity and -NH2 electronegativity to optimize the coordination environment and inhibit HER. Through theoretical screening, tris(hydroxymethyl)aminomethane (TRIS) was identified as the optimal additive due to its superior electrostatic potential and balanced steric profile. Spectroscopic, electrochemical, and theoretical analyses demonstrate that TRIS, with its multiple electronegative sites, can act as a structural node to reconstruct hydrogen-bond networks and immobilize water. Simultaneously, TRIS adsorbs onto the electrode surface, where its nucleophilic -NH2 groups penetrate the chromium solvation shell to facilitate ion transport. Consequently, an ICFB with 20 mM TRIS achieved 83.30% energy efficiency at 140 mA/cm2. This work offers a scalable solution for high-performance stationary energy storage.
The spatial distribution of active sites in metal-supported catalysts is intrinsically governed by the competitive interplay between metal-metal and metal-support interactions. Conventional stabilization strategies fail to achieve atomic dispersion and suppress sintering when metallic cohesive forces dominate. Herein, alkali metal ions (Li+, Na+, and K+) were employed as sacrificial single-ion templates to construct well-defined Au–N coordination microenvironments on carbon supports via a synergistic co-solidification strategy, followed by chemical leaching to eliminate the templates. These generated docking sites facilitate the precise allocation of isolated Au single sites, thereby constructing a thermally stable architecture that effectively resists aggregation. In addition, the local pyridinic Au–N coordination strengthens the adsorption of key reaction intermediates, thereby enhancing catalytic performance in acetylene hydrochlorination. Consequently, a high acetylene conversion of 92.3% and a vinyl chloride selectivity of up to 99.0% are simultaneously achieved, along with excellent long-term operational durability exceeding 160 h. Overall, this work provides a general and facile strategy to anchor single-site metal catalysts on activated carbon supports, mitigating aggregation and enabling high-performance catalysis with long-term stability.
Efficient conversion of renewable lignocellulosic biomass into high-value chemicals and liquid fuels is central to the global carbon-neutrality agenda. However, the raw bio-oil obtained from biomass typically exhibits low heating value and poor stability due to high oxygen content. Selective hydrodeoxygenation (HDO) is indispensable for fuel upgrading but requires precise control over competitive C-O and C-C bond cleavage to prevent carbon loss. Herein, we report a strategy to decouple catalytic activity from structural degradation in Ni3P phosphides via Pd-mediated electronic and geometric engineering. A ternary NiPdP catalyst exhibits > 97% selectivity toward cycloalkanes with negligible C-C scission at 200 °C using m-cresol and anisole as representative bio-oil oxygenates. Synchrotron X-ray absorption fine structure (XAFS) and high-resolution transmission electron microscopy (HRTEM) analyses reveal that Pd incorporation induces significant lattice strain and compressive distortion, while H2-temperature programmed reduction (H2-TPR) suggests a Pd-assisted hydrogen activation process that favors the formation of ultrafine nanocrystals (< 10 nm). This work clarifies the role of noble-metal-induced strain in optimizing the metal-acid bifunctionality of phosphides, offering a fundamental basis for designing sintering-resistant catalysts for efficient biorefining and sustainable biofuel production.
Achieving the selective catalytic dimerization of the branched olefin via solid superbases remains a challenging yet sustainable strategy. In this study, a series of K/K2CO3 solid superbase catalysts were rapidly prepared via the melt-loading method for the dimerization of isobutene (IBE) to 2,4,4-trimethyl-1-pentene (TP1). Carbonate vacancy concentration was readily tuned by regulating the pretreatment temperature of K2CO3. The screened 5%K/K2CO3-430 °C catalyst, containing an appropriate amount of carbonate vacancies, achieved an isobutene conversion of 49.8% and a TP1 selectivity of 80.9% under mild conditions (190 °C, 15 h), significantly outperforming conventional solid acid catalysts. Characterization results demonstrate that the carbonate vacancies (anion lattice defects) induced by optimal pretreatment temperature generate more coordinatively unsaturated oxygen (CUO) sites on the surface. These sites substantially strengthen the metal-support interaction (MSI, in a broad sense) between K and K2CO3, thereby enhancing the electron-donating ability of the superbasic sites. Density functional theory (DFT) calculations further reveal that the loaded metallic K promotes electron transfer to IBE through electron density redistribution and the semi-encapsulation configuration of K atoms in tri-oxygen hollow sites, enabling efficient activation of isobutene. In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) detects allylic anion intermediates, confirming that the reaction proceeds via a radical-anion pathway. This study provides a facile approach for the efficient preparation of solid superbases and the construction of defect engineering in catalysts, offering new insights into the design of high-performance catalysts for green olefin conversion.
Engineering the electron transfer pathway in metal-organic frameworks (MOFs) is crucial for photocatalytic nitrogen fixation. This study proposes a metal-nonmetal co-doping strategy to interconnect the metal-to-metal charge transfer (MMCT) pathway with the ligand-to-metal charge transfer (LMCT) pathway in Ti-based MOFs for boosted electron transfer. A series of B and Co co-doped NH2-MIL-125, denoted as NBM(Ti/Co), were designed and synthesized by a one-pot hydrothermal method. In the NBM(Ti/Co), the doped B atom with the electron-deficient property promotes the electron transfer through the ligand to the metal node pathway, while the doped Co2+ with a lower ionization energy than Ti4+ opens up an inter-metal electron transfer pathway. These two pathways converge at the Ti4+ active site, generating an integrated B–Co–Ti electron-transfer network that shuttles photogenerated electrons, facilitating the charge separation and migration. The optimal NBM(Ti/Co) sample achieves a high ammonia production rate of 379.2 μmol/(g·h) under full-spectrum irradiation, which is 4.2-fold greater than that of pristine NH2-MIL-125. This study opens an avenue to designing high-performance MOF-based photocatalysts through a metal-nonmetal co-doping strategy.
Agriculture wastewater always contains amounts of pesticides as well as eutrophic element which induces serious environmental hazard, so that the development of an efficient, economical, and sustainable approach becomes the pursuit goal by worldwide researchers. Coagulation is one of the most facile treatment technologies for the removal of colloidal impurities from water, but it is limited in the separation of dissolved organic matter (DOM) and inorganic salt. In this study, we introduced an organic-inorganic hybrid coagulants (PTyTS) that can self-assembly form aggregates with special hydrophobic core and hydrophilic shell structure in water, which can be used as a platform to remediate agriculture wastewater. The PTyTS reached an excellent coagulation performance for the removal of emamectin benzoate (EB, a typical pesticide, 58.1%), nitrate nitrogen (NO3−-N, 23.1%), and total phosphorus (TP, 92.3%). The strategy utilized a mechanism in which hydrophobic pesticides are solubilized into the cores and hydrophilic eutrophic elements are adsorbed on the shells, enabling rapid aggregation and removal. This approach provided a simple and effective pathway to address a broad spectrum of organic and inorganic contaminant pollution from wastewater.
Sustainable management of phosphate-laden wastewater requires functional materials that pair efficient removal with practical recyclability. Here, a magnesite-modified seaweed hydrochar–chitosan composite hydrogel bead (Mg@SHC/CS) was prepared by combining hydrothermal carbonization of marine biomass waste with chitosan-mediated gelation, converting two low-cost feedstocks into a shaped and recoverable adsorbent. The resulting beads exhibited a hierarchically porous structure, rapid phosphate uptake under near-neutral conditions, good tolerance toward common competing anions, and stable regeneration, retaining 87.03% of the initial adsorption capacity after five adsorption–desorption cycles. Equilibrium data were best described by the Sips model, with the maximum adsorption capacity increasing from 73.41 to 85.35 mg P/g as the temperature rose from 298 to 318 K. Site energy distribution (SED) analysis confirmed preferential occupation of high-energy sites at low coverage, in line with energetically heterogeneous binding under a finite-capacity constraint. Spectroscopic characterization combined with density functional theory (DFT) and independent gradient model based on Hirshfeld partition (IGMH) calculations revealed that phosphate immobilization was governed mainly by Mg–O centers, carboxyl groups, and amino/ammonium functionalities through inner-sphere complexation, ligand exchange, hydrogen bonding, and electrostatic interactions. Cradle-to-gate life cycle assessment (LCA) identified chitosan and Mg@SHC precursor preparation as the principal environmental hotspots, pointing to priorities for greener process design. These results establish Mg@SHC/CS as an effective, recyclable adsorbent for phosphate recovery and provide mechanistic and preparation-stage sustainability insights for the design of waste-derived water treatment materials.
Developing high-efficiency air filters capable of withstanding complex contaminants such as oily aerosols and high humidity without irreversible fouling remains a formidable challenge. Herein, a robust, fluorine-free superhydrophobic nanofiber membrane (MO/PVDF) was fabricated by synergizing moisture-induced phase separation with thiol-ene click chemistry. This dual-strategy approach constructed a hierarchically rough architecture stabilized by covalently grafted hydrophobic molecular brushes. The resulting membrane exhibits a water contact angle > 151° and robust repellency towards low-surface-tension liquids including ethylene glycol. This effectively inhibits the capillary wicking of oily particulate matter, thereby transforming the filtration mechanism from a failure-prone depth filtration regime to a sustainable surface filtration mode. Consequently, the membrane maintains a filtration efficiency > 99.7% for oily PM0.3 (particulate matter in the air with a diameter less than or equal to 0.3 μm) with a minimal increase in pressure drop. Under high-humidity conditions, the engineered low-adhesion surface facilitates a transition from film-wise to drop-wise condensation, enabling a spontaneous self-cleaning effect. Furthermore, in industrial-scale pulse-jet dust filtration tests, the membrane demonstrates exceptional fouling reversibility and a passive cake detachment mechanism, retaining a high dust stripping efficiency (> 86%) and structural integrity after 10,000 aging cycles. This work establishes a scalable and fluorine-free interfacial design paradigm for next-generation air filtration media operating under harsh, oily, and humid environments.
Developing stable lithium–sulfur (Li–S) batteries with high areal capacities is a prerequisite for their commercialization. However, suppressing the polysulfide shuttle and maintaining efficient ion transport under high sulfur loadings (> 10 mg/cm2) remains a challenge. Here, a facile, scalable, and sustainable one-step carbonization strategy was developed to upcycle waste textiles into high-performance carbon cloth (HPC) with tunable graphitization. The optimized HPC950 framework features a unique, ordered three-dimensional (3D) conductive carbon fiber network and a porous architecture. Benefiting from the synergistic integration of high intrinsic conductivity and a specialized pore size with “ion-confinement effect”, the resulting electrode effectively mitigates polysulfide shuttling while ensuring rapid Li+ transport. Consequently, the HPC950/S cathode shows stable cycling, retaining a capacity of 4.89 mAh/cm2 at a sulfur loading of 8.51 mg/cm2 over 230 cycles and 6.89 mAh/cm2 at 10.34 mg/cm2. The practical viability is further validated by powering a 33 light-emitting-diode (LED) array with high-load coin cells. This cost-effective and sustainable textile-derived carbon cloth provides a compelling pathway for next-generation high-performance Li–S batteries.
Palladium single-atom catalysts show exceptional catalytic performance in nitrile butadiene rubber (NBR) hydrogenation due to their unique unsaturated coordination environments. However, the hydrogenation activity and atomic efficiency are seriously limited by inherent instability of undercoordinated Pdδ+ sites and poor support structure, leading to decreased hydrogenation degree and cycling stability. In this work, a novel single-atom palladium catalysts was developed, where undercoordinated single-atom Pdδ+ sites are steadily anchored onto CeO2-x nano-islands supported by SiO2 (Pd1/CeO2-x/SiO2). The strong metal-interaction of CeO2-x nano-islands immobilize the undercoordinated Pdδ+ sites to enhance adsorption of olefin bonds in NBR, while SiO2 promotes mass transfer diffusion of NBR and atomic efficiency of palladium. The Pd1/CeO2-x/SiO2 thus achieves an unprecedented hydrogenation degree of up to 99.8% without decrease over a 10-runs stability test in selective hydrogenation of NBR, outperforming previously state-of-the-art catalysts. Consequently, this work will offer a new strategy for single-atom catalysts to achieve high steady-state activity in selective hydrogenation.
Lithium diisopropylamide (LDA)-mediated aldol condensation between esters and electrophiles (e.g., aldehydes, ketones) represents a versatile route to β-hydroxy esters. However, ester enolates, particularly those derived from ethyl acetate (EA), are highly reactive and prone to self-condensation and decomposition. These intrinsic limitations necessitate cryogenic conditions, thereby increasing energy consumption and limiting scalability. Herein, we reported a continuous-flow strategy that enabled LDA-mediated aldol condensation of EA at room temperature, affording good to excellent yields within 1.5 s at an equimolar ester-to-electrophile ratio. Using 3-pyridine aldehyde as a model electrophile, batch studies revealed that minimizing the residence time of the enolate was critical for improving yield. Nevertheless, even under optimized batch conditions, yields remained limited at room temperature (10% with 1.2 equivalents (eq.) of LDA and 32% with 2.0 eq.). In contrast, the continuous-flow approach, enabled by rapid micromixing and precise residence time control, facilitated near-quantitative enolate formation and afforded the corresponding β-hydroxy ester in near-quantitative yield using only 1.2 eq. of LDA. The characteristic micromixing time required for EA deprotonation, and the optimal residence time range for efficient enolate formation were identified. This strategy exhibited broad substrate scope, accommodating electrophiles both with and without acidic α-protons, and was further extended to the aldol condensation of carboxylic acids. Furthermore, downstream functionalizations of EA-derived β-hydroxy esters can be efficiently performed directly on the crude product following solvent removal by vacuum distillation, obviating the need for intermediate purification. Overall, this work established a robust, operationally simple, and energy-efficient platform for LDA-mediated aldol condensation of EA.
To advance the development of high-performance rechargeable zinc-air batteries (ZABs) with efficient oxygen electrochemistry, significant progress is needed in research on Fe-based nanoparticle/single-atom bifunctional oxygen electrocatalysts. Nevertheless, the structure-activity relationship and synergy mechanism of Fe-based nnoparticle/single-atom hybrid catalysts are not well-known. Herein, Self-supported carbon nanofiber electrocatalysts with in-situ synthesized FeS, Fe2P, or Fe3C nanoparticles and atomically dispersed Fe-Nx sites were prepared in this work by the coaxial electrospinning method. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) simulations showed that there was a significant change in charge distribution, an increase in the adsorption of *O intermediates, and a decrease in the *OH desorption energy barrier at the FeS/FeSA interface. It can be concluded that FeS/FeSA has better electronic and adsorption properties than Fe2P/FeSA and Fe3C/FeSA. Therefore, FeS/FeSA has an oxygen reduction reaction (ORR) half-wave potential of 0.89 V and an oxygen evolution reaction (OER) overpotential of 240 mV at 10 mA/cm2, which is relatively high compared with that of Fe2P/FeSA (0.79 V, 260 mV) and Fe3C/FeSA (0.77 V, 250 mV), and it has a small potential gap (ΔE) of 0.58 V. FeS/FeSA can be used as the air cathode in liquid ZABs; it has a high peak power density of 116 mW/cm2 and is stable for more than 150 hours. The above results have laid the foundation for the construction of high-performance air cathode catalysts by means of effective coupling of atomic nanoparticles and shown the direction for developing high-efficiency, long-life rechargeable zinc-air batteries.
The solubility of fluorinated refrigerants (FRs) in ionic liquids (ILs) plays a critical role in IL-based absorption separation processes for the mitigation of greenhouse gases. In this work, the thermodynamic performance of the fully predictive COSMO-RS model is comprehensively assessed using an extensive dataset comprising 3853 experimental FR-in-IL solubility data points covering hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and other FR types. The results indicate that COSMO-RS generally captures qualitative solubility trends across diverse refrigerant-IL combinations, though notable quantitative deviations exist for specific systems. An empirical linear correction strategy is applied to reduce systematic biases, achieving significant accuracy improvements particularly for systems exhibiting approximately linear prediction deviations. Based on the evaluated prediction capability, a modeling-driven screening of ILs for the capture of R-134a, a high-GWP refrigerant, is conducted based on absorption capacity (AC), desorption ease (DE), and critical physical properties. Three acetate-based ILs, namely [P4442][Ac], [P4441][Ac], and [pmpy][Ac], are identified as promising candidates from a predictive perspective. Mechanistic insights derived from molecular simulations, including σ-profile and interaction energy analyses, reduced density gradient (RDG) visualization, and molecular dynamics (MD) calculations, reveal that the absorption behavior of R-134a in ILs arises from the combined effects of anion–refrigerant hydrogen-bonding interactions and cation-dependent van der Waals interactions. Overall, this study highlights the potential of predictive thermodynamic modeling combined with systematic screening as a useful framework for guiding IL selection in FR capture and greenhouse gas mitigation.
Although electrical energy storage and microfluidic systems employing electrically responsive ionic media such as ionic liquids (ILs) have seen substantial progress, the mechanisms by which ion migration and adsorption at electrochemically controlled interfaces dictate wettability and triboelectric behavior remain elusive. In this work, we investigated the interfacial adsorption and friction behaviors of two ILs containing imidazolyl chains and imidazolylamino cations on charged, organosilicon-modified Au surfaces. The mechanisms of ion migration and adsorption were further elucidated through molecular dynamics simulations. Notably, the two ILs exhibited opposite friction responses under negative electrical potentials, revealing an ion-specific electro-responsive behavior. This difference arises from the interplay of van der Waals attractions, electrostatic interactions, and short-range forces, which collectively govern wetting strength and dominate the dissipation of sliding energy. Furthermore, a semi-quantitative correlation between nanofriction and ILs wettability under applied potentials was established, highlighting the critical role of molecular structure design in enabling tunable electro-responsive friction. By identifying key molecular and interfacial parameters that control electro-responsive friction, this work provides strategies for optimizing surface functionalization, ionic liquid selection, and applied potentials in electro-lubrication systems, while establishing molecular-level design rules for electrically tunable interfaces with broad implications for micro/nanofluidics, electrowetting, soft robotics, and energy-storage applications.
Oral squamous cell carcinoma (OSCC) ranks among the most common malignant neoplasms affecting the oral cavity. Conventional treatments like surgery and chemotherapy often cause severe side effects and a poor prognosis. Photodynamic therapy (PDT), characterized by its non-invasive nature, high specificity, and minimal invasiveness, has shown promise as an alternative therapeutic approach. The fundamental principle underlying PDT is a photochemical reaction: photosensitizers (PSs) are activated by light at specific wavelengths to generate reactive oxygen species (ROS), ultimately resulting in cancer cell death. However, the clinical translation of PDT for OSCC is hindered by two critical challenges: most conventional PSs rely on complex synthetic routes, leading to high synthesis costs and low yields; additionally, traditional Type II PSs are highly susceptible to the hypoxic OSCC microenvironment, compromising therapeutic efficacy. The D-π-A molecular engineering strategy is a common approach in developing new PSs, where π-bridges are often constructed using various synthetic heterocycles that further increase synthetic complexity. To address these dual challenges, we introduced natural purine (a readily available, structurally simple heterocycle) as the π-bridge in the D-π-A framework and modified its C8 position with various electron-withdrawing acceptors via straightforward synthetic steps, leading to the development of an efficient PS (PCP) that operates via a Type I mechanism. PCP exhibited remarkable efficacy in the photodynamic ablation of tumor tissues and potently suppressed OSCC proliferation in both in vitro and in vivo settings, while also demonstrating favorable biocompatibility. The strategy of employing natural heterocycles (purine) simplifies the synthesis of high-performance PSs and establishes a promising foundation for advancing PDT in OSCC therapy, overcoming the key bottlenecks of conventional PSs.
The conventional development of high-performance catalysts for antibiotic degradation often relies on resource-intensive trial-and-error methods, highlighting a critical bottleneck in green process design. Therefore, this study develops an interpretable machine-learning framework to enable rapid, low-cost, and efficient antibiotic degradation via PMS activation with iron-based oxide catalysts. A high-quality dataset of 1,022 experimental records is constructed to investigate the structure-activity relationships of catalyst properties. Six machine learning models are automatically optimized using the Optuna framework, with CatBoost (CAB) identified as the optimal predictor (test-set R2 = 0.9595). The interpretability of the CAB model is deciphered through Shapley additive explanations and partial dependence plots, revealing reaction time, drug, pH, PMS concentration, and catalyst dosage as the most critical features governing degradation efficiency. Finally, the preferred model integrated with the NSGA-III algorithm is employed to resolve the efficiency-cost-time trilemma, simultaneously maximizing degradation rate while minimizing reaction time and PMS consumption. The optimized MnFe2O4/CuS and Fe3O4/MoS2 catalysts achieve degradation rates of 96.15% and 94.51% for lomefloxacin hydrochloride and ofloxacin, within a 25.01-minute reaction time and at a PMS concentration of 0.14 mM, which are significantly superior to the reported values. This work establishes a data-driven paradigm for green chemical engineering, offering a novel toolkit for the rational and sustainable design of advanced oxidation processes with minimized resource footprint.
Water scarcity affects the survival of over 2.2 billion people worldwide, emerging as a pressing global challenge. Atmospheric water harvesting based on porous adsorbents presents a promising solution to this crisis. However, the current adsorption materials exhibit quite low capturing capacity under extremely low atmospheric humidity. Herein, we synthesized a class of M-gallate (M = Mg, Co, and Ni) metal-organic frameworks (MOFs) and evaluated their atmospheric water harvesting performance. Impressively, Mg-gallate MOF was stable for at least 28 days in water, and exhibited exceptional water uptake capacity of 170.0 mg/g at 0.2% relative humidity (RH) and 178.6 mg/g at 2.6% RH, which exceeds the highest value of the previously reported porous materials under the same conditions. Even at 5.0% RH, its water adsorption capacity is lower than that of the record-breaking water-stable Ni2Cl2BBTA. Spectral studies and DFT calculations suggest that the water adsorption process follows a multi-layer mechanism. The main driving forces underlying the outstanding atmospheric water harvesting performance of the MOF are the hydrogen bonding interactions between water molecules and the oxygen-containing functional groups (carboxylate and phenolic-OH) in MOF framework, the hydrogen bonding among adsorbed water molecules, and the synergistic effect of pore filling. Thus, the strategy developed here provides a simple and effective way for the development of high-performance atmospheric water adsorbents under ultra-low humidity environments.
Cold plasma is an emerging electrified, reagent-free technology with strong potential for green chemical engineering. However, its integration into automated flow systems converting industrial wastewater into nutrient-rich fertigation media remains limited. Here, we demonstrate an automated microbubble-enhanced cold plasma activation (MB-CPA) process as a Power-to-X strategy for simultaneous wastewater treatment and plant-growth promotion in commercial hydroponics. A programmed plasma activation (automated MBCPA) module integrating a cavitation tube (1 and 2 h day-1 at 28 W) significantly enhanced germination, shoot length, biomass, and chlorophyll of garlic seedlings compared with microbubble-only and untreated controls, owing to fertilizing plasma-generated reactive oxygen and nitrogen species (RONS). The optimized MB-CPA was applied to food-processing (malting) wastewater supplying the hydroponic loop. The plasma treated wastewater yielded >10% higher germination, >1.6-fold plant length, >1.9-fold biomass, and > 10-fold chlorophyll content than the control and low-plasma treatments. MB-CPA reduced chemical oxygen demand by ∼90% and turbidity by ∼98%, while increasing total nitrogen to 53.1 mg/L and establishing a favourable C:N ratio (2.3-18) that supported vigorous growth, consistent with plasma-assisted nitrogen fixation and enhanced bioavailability of NO3− and NO2−. Plasma-exposed plants showed systematic reactive oxygen species generation in roots, a 1.2-fold up-regulation of proline and higher uptake of nitrogen (NO3−, NH4+) and macro/micronutrients, indicating a regulated stress response and elevated metabolic activity rather than oxidative damage. Our results demonstrate that automated MB-CPA is a dual-function green chemical engineering process upgrading industrial wastewater into a fit-for-purpose fertigation medium for boosting hydroponic crop performance that can partially displace agrochemical inputs.
The selective capture of alkali metal ions in complex systems has consistently been an important but challenging subject in the field of separation science. In this work, three crown ether functionalized ionic liquids (CE-FILs), namely 1-capryl benzo-12-crown-4 ether 3-methylimidazole bis(trifluoromethanesulfonyl)imide ([C8(B12C4)mim][NTf2]), 1-capryl benzo-15-crown-5 ether 3-methylimidazole bis(trifluoromethanesulfonyl)imide ([C8(B15C5)mim][NTf2]), and 1-capryl benzo-18-crown-6 ether 3-methylimidazole bis(trifluoromethanesulfonyl)imide ([C8(B18C6)mim][NTf2]) have been obtained for selective capture of alkali metal ions. Their structures and interactions with alkali metal ions have been investigated. The results reveal that [C8(B12C4)mim][NTf2] exhibits the highest selectivity for Na+ with a high Na+/Li+ selectivity of 1810. In contrast, both [C8(B15C5)mim][NTf2] and [C8(B18C6)mim][NTf2] demonstrate the most favorable binding affinity for K+ over other alkali metal ions. It is noteworthy that [C8(B18C6)mim][NTf2] also shows remarkable selectivity for Rb+ and Cs+ over Na+ and Li+. The chelation-driven process between CE-FILs and alkali metals is governed by host-guest compatibility, ionic hydration energy, and interfacial behavior. The spectroscopic characterization and density functional theory (DFT) calculation all support that the interaction of the three CE-FILs with alkali metals involves ion-dipole interaction, hydrogen bonding, and electrostatic interaction.
