Metabolic perturbation and oxidative damage induced by tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-ethylhexyl) phosphate (TEHP) on Escherichia coli through integrative analyses of metabolome.

Organophosphate esters (OPEs) are one of the emerging environmental threats, causing the hazard to ecosystem safety and human health. Yet, the toxic effects and metabolic response mechanism after Escherichia coli (E.coli) exposed to TDCIPP and TEHP is inconclusive. Herein, the levels of SOD and CAT were elevated in a concentration-dependent manner, accompanied with the increase of MDA contents, signifying the activation of antioxidant response and occurrence of lipid peroxidation. Oxidative damage mediated by excessive accumulation of ROS decreased membrane potential and inhibited membrane protein synthesis, causing membrane protein dysfunction. Integrative analyses of GC-MS and LC-MS based metabolomics evinced that significant perturbation to the carbohydrate metabolism, nucleotide metabolism, lipids metabolism, amino acid metabolism, organic acids metabolism were induced following exposure to TDCIPP and TEHP in E.coli, resulting in metabolic reprogramming. Additionally, metabolites including PE(16:1(5Z)/15:0), PA(17:0/15:1(9Z)), PC(20:2(11Z,14Z)/12:0), LysoPC(18:3(6Z,9Z,12Z)/0:0) were significantly upregulated, manifesting that cell membrane protective molecule was afforded by these differential metabolites to improve permeability and fluidity. Overall, current findings generate new insights into the molecular toxicity mechanism by which E.coli respond to TDCIPP and TEHP stress and supply valuable information for potential ecological risks of OPEs on aquatic ecosystems.

Construction of Fe3O4/xSiO2/ySiO2 Nanoparticles for Pesticide Removal from Water: Improved Dispersion Stability and Adsorption Capacity.

Highly efficient and reusable adsorbents for pesticide removal from wastewater have received increasing attention. In this study, Fe3O4 was synthesized using the solvothermal method. Fe3O4/xSiO2 and Fe3O4/xSiO2/ySiO2 were obtained through layer-by-layer silica (SiO2) coating on the surface of Fe3O4. SiO2 coating improved the dispersibility of the adsorbent, which can be separated from water rapidly under the action of the external magnetic field. The adsorption capacity of the adsorbent was investigated through removing pyraclostrobin from synthetic wastewater. The adsorbent showed the highest adsorption effect at the adsorbent concentration of 1 mg mL-1, at a pH of 7, and the adsorbent time of 110 min. The fitting model of the adsorption process conformed to the second-order kinetic model and the Langmuir model. The maximum adsorption capacity of Fe3O4/xSiO2/ySiO2 nanoparticles was 94.89 mg g-1, and the removal efficiency was about 96% at adsorption equilibrium. Acetone as the eluent can effectively desorb the adsorbent, and the desorbed adsorbent had high reusability. Particularly, the removal efficiency was still greater than 86% after 9 times of reuse. These results provide a reference for designing reusable nanoparticles to effectively absorb pesticides in wastewater.

Efficient removal of Cr(VI) by a 3D Z-scheme TiO2-ZnxCd1-xS graphene aerogel via synergy of adsorption and photocatalysis under visible light.

Efficient and robust photocatalysts for environmental pollutants removal with outstanding stability have great significance. Herein, we report a kind of three dimensional (3D) photocatalyst presented as Z-scheme heterojunction, which combining TiO2 and ZnxCd1-xS with graphene aerogel to contrast TiO2-ZnxCd1-xS graphene aerogel (TSGA, x=0.5) through a moderate hydrothermal process. The as-prepared Z-scheme TSGA was used to remove aqueous Cr(VI) via a synergistic effect of adsorption and visible light photocatalysis. The adsorption equilibrium can be reached about 40 min, then after about 30 min irradiation under visible light (wavelength (λ) > 420 nm) the removal rate of Cr(VI) almost reached 100%, which is much better than the performance of pristine TiO2 and Zn0.5Cd0.5S, as well as TiO2 graphene aerogel (TGA) and Zn0.5Cd0.5S graphene aerogel (SGA). The virulent Cr(VI) was reduced to Cr(III) with hypotoxicity after photocatalysis on TSGA, meanwhile the as-synthesized TSGA presented a good stability and reusability. The reduced graphene oxide (rGO) sheets between TiO2 and Zn0.5Cd0.5S played a role as charge transfer mediator, promoting the photoinduced electrons transfer and photocatalysis ability of TSGA was enhanced significantly. Hence, such photocatalyst exhibits a potential application on removing heavy metals with high efficiency and stability from polluted aqueous environment.

Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO2 ternary composites: Adsorption performance and mechanism.

Because of its significant toxicological effects on the environment and human health, arsenic (As) is a major global issue. In this study, an Fe-based metal-organic framework (MOF) (Materials of Institut Lavoisier: MIL-100 (Fe)) which was impregnated with reduced graphene oxide (rGO) by using a simple hydrothermal method and coated with birnessite-type manganese oxide (δ-MnO2) using the one-pot reaction process (MIL-100(Fe)/rGO/δ-MnO2 nanocomposites) was synthesized and applied successfully in As removal. The removal efficiency was rapid, the equilibrium was achieved in 40 min and 120 min for As(III) and As(V), respectively, at a level of 5 mg/L. The maximum adsorption capacities of As(III) and As(V) at pH 2 were 192.67 mg/g and 162.07 mg/g, respectively. The adsorbent revealed high stability in pH range 2-9 and saturated adsorbent can be fully regenerated at least five runs. The adsorption process can be described by the pseudo-second-order kinetic model and Langmuir monolayer adsorption. The adsorption mechanisms consisted of electrostatic interaction, oxidation and inner sphere surface complexation.

Construction and biological effects of a redox-enzyme dual-responsive lufenuron nano-controlled release formulation.

BACKGROUND: Pesticide formulations based on nanotechnology can effectively improve the efficiency of pesticide utilization and reduce pesticide residues in the environment. In this study, mesoporous silica nanoparticles containing disulfide bonds were synthesized by the sol-gel method, carboxylated and adsorbed with lufenuron, and grafted with cellulose to obtain a lufenuron-loaded nano-controlled release formulation (Luf@MSNs-ss-cellulose). RESULTS: The structure and properties of Luf@MSNs-ss-cellulose were characterized. The results showed that Luf@MSNs-ss-cellulose exhibits a regular spherical shape with 12.41% pesticide loading. The highest cumulative release rate (73.46%) of this pesticide-loaded nanoparticle was observed at 7 days in the environment of glutathione and cellulase, which shows redox-enzyme dual-responsive performance. As a result of cellulose grafting, Luf@MSNs-ss-cellulose had a small contact angle and high adhesion work on corn leaves, indicating good wetting and adhesion properties. After 14 days of spraying with 20 mg L-1 formulations in the long-term control efficacy experiment, the mortality of Luf@MSNs-ss-cellulose against Ostrinia furnacalis larvae (56.67%) was significantly higher than that of commercial Luf@EW (36.67%). Luf@MSNs-ss-cellulose is safer for earthworms and L02 cells. CONCLUSION: The nano-controlled release formulation obtained in this study achieved intelligent pesticide delivery in time and space under the environmental stimulation of glutathione and cellulase, providing an effective method for the development of novel pesticide delivery systems. © 2023 Society of Chemical Industry.

A biodegradable oxidized starch/carboxymethyl chitosan film coated with pesticide-loaded ZIF-8 for tomato fusarium wilt control.

Film mulching is one of the most important methods to control soil-borne diseases. However, the traditional mulch may cause microplastic pollution and soil ecological damage. Herein, a biodegradable film was developed using oxidized starch and carboxymethyl chitosan and incorporated ZIF-8 carrying fludioxonil to sustainably control soil-borne disease. The microstructure, mechanical properties, optical properties, and water barrier properties of the composite films (Flu@ZIF-8-OS/CMCS) were investigated. The results show that Flu@ZIF-8-OS/CMCS had a smooth and uniform surface and excellent light transmittance. The excellent mechanical properties of the films were verified by tensile strength, elongation at break and Young's modulus. Higher contact angle and lower water vapor permeability indicate water retention capacity of the soil was improved through using Flu@ZIF-8-OS/CMCS. Furthermore, the release properties, biological activity, degradability and safety to soil organisms of Flu@ZIF-8-OS/CMCS was determined. The addition of ZIF-8 significantly improved the film's ability to retard the release of Flu, while the Flu@ZIF-8-OS/CMCS has good soil degradability. In vitro antifungal assays and pot experiments demonstrated excellent inhibitory activity against Fusarium oxysporum f. sp. Lycopersici. Flu@ZIF-8-OS/CMCS caused only 13.33 % mortality of earthworms within 7 d. This research provides a new approach to reducing microplastic pollution and effectively managing soil-borne diseases.

One-step synthesis of nitrogen-functionalized graphene aerogel for efficient removal of hexavalent chromium in water.

The efficient removal of hexavalent chromium (Cr(VI)) with high toxicity has attracted widespread concern since it causes serious harm to ecological environment and public health. Herein, we report a novel nitrogen-functionalized graphene aerogel with stereoscopic structure through a simple hydrothermal method and freeze drying for Cr(VI) removal from water. Graphene oxide (GO) and nitrogenous organics polyethyleneimine (PEI) and pyrrole are used as raw materials for preparing PEI/polypyrrole/GO aerogel (PPGA) adsorbent. PEI and pyrrole act as nitrogen sources to introduce nitrogenous functional groups, and also take on the role of cross-linkers for helping GO sheets to form stereoscopic structure. The obtained PPGA has a fast adsorption rate, excellent reusability, and shows a remarkable adsorption capacity for Cr(VI) up to 458.24 mg/g under the optimal conditions (pH 2.0, 298 K, Cr(VI): 600 mg/L, dosage: 0.4 g/L). The adsorption process of Cr(VI) on PPGA can fit the pseudo-second-order kinetic model well. Analysis of intraparticle diffusion shows that the Cr(VI) removal process is a multi-step process. Adsorption thermodynamic and isotherm results demonstrate Cr(VI) adsorption on PPGA is a spontaneous endothermic process. The adsorption mechanism involves electrostatic attraction, redox, and chelation. In general, this work provides a simple and eco-friendly way to prepare PPGA, which has a great potential for actual application of Cr(VI) removal in effluent.

Sodium alginate-carboxymethyl chitosan hydrogels loaded with difenoconazole for pH-responsive release to control wheat crown rot.

Increasing concern about environmental pollution has driven the development of controlled release formulations for agrochemicals. Due to the advantages of degradability and responsiveness to environmental stimuli, polysaccharide-based hydrogel is an ideal carrier for agrochemicals controlled release. In this study, a method-easy polysaccharide hydrogel for controlled release of difenoconazole (DZ) was prepared with sodium alginate (SA) and carboxymethyl chitosan (CMCS). Due to its three-dimensional crosslinked mesh structure, the prepared hydrogels (CSDZ) showed an agrochemical load capacity of 9.03 % and an encapsulation efficiency of 68.64 %. The release rate is faster in alkaline solution, followed by neutral solution, and slowest in an acid environment, which is consistent with the swelling behavior. Furthermore, leaching studies showed that CSDZ hydrogels have excellent protective properties for encapsulated agrochemicals. Compared with technical DZ, the results of in vitro and pot antifungal testing showed that CSDZ had a better control effect against wheat crown rot (Fusarium pseudograminearum). Safety assessment studies indicated that CSDZ hydrogels exhibit good biocompatibility on nontargeted organisms (Daphnia magna, zebrafish and Eisenia fetida) and wheat. This study aims to provide a potentially promising approach for the preparation and application of biocompatible polysaccharide-based hydrogels for agrochemical-controlled release in sustainable disease management.

Surface oxygen vacancies and carbon dopant co-decorated magnetic ZnFe2O4 as photo-Fenton catalyst towards efficient degradation of tetracycline hydrochloride.

Carbon doped strategy has been recognized as an efficient strategy to enhance photo-Fenton degradation performance. However, the preparation of high efficiency C-doped photocatalyst has been a significant challenge. Herein, we synthesized magnetic carbon-doped ZnFe2O4 via a facile solvothermal-calcination route. The photo-Fenton activity of C-doped ZnFe2O4 under visible light (λ > 420 nm) was evaluated by degradation of tetracycline hydrochloride. C-doped sample, CZF-2 (0.5 g L-1) presented excellent removal performance for TC-HCl (20 mg L-1) in presence of H2O2 (10 mM) and could remove 90.8% of TC-HCl within 50 min. The C-doping modulates crystal defects and generates surface oxygen vacancies simultaneously, thus building a new C-doping level near valence band and a defect level under the conduction band. Meanwhile, surface oxygen vacancies bring photo-generated electrons and electrons generated from itself to surface to accelerate photo-Fenton reaction, and the holes are rapidly transferred to the surface to participate in the degradation of pollutants.

Construction of Prochloraz-Loaded Hollow Mesoporous Silica Nanoparticles Coated with Metal-Phenolic Networks for Precise Release and Improved Biosafety of Pesticides.

Currently, environmental-responsive pesticide delivery systems have become an essential way to improve the effective utilization of pesticides. In this paper, by using hollow mesoporous silica (HMS) as a nanocarrier and TA-Cu metal-phenolic networks as a capping agent, a pH-responsive controlled release nano-formulation loaded with prochloraz (Pro@HMS-TA-Cu) was constructed. The structure and properties of Pro@HMS-TA-Cu were adequately characterised and analysed. The results showed that the loading content of Pro@HMS-TA-Cu nanoparticles was about 17.7% and the Pro@HMS-TA-Cu nanoparticles exhibited significant pH-responsive properties. After a coating of the TA-Cu metal-phenolic network, the contact angle and adhesion work of Pro@HMS-TA-Cu nanoparticles on the surface of oilseed rape leaves after 360 s were 59.6° and 107.2 mJ·m-2, respectively, indicating that the prepared nanoparticles possessed excellent adhesion. In addition, the Pro@HMS-TA-Cu nanoparticles demonstrated better antifungal activity against Sclerotinia sclerotiorum and lower toxicity to zebrafish compared to prochloraz technical. Hence, the pH-responsive nanoparticles prepared with a TA-Cu metal-phenolic network as a capping agent are highly efficient and environmentally friendly, providing a new approach for the development of new pesticide delivery systems.

Multiscale structural regulation of metal-organic framework nanofilm arrays for efficient oxygen evolution reaction.

Novel MOF nanofilm arrays (NiCoBDC-Fc) were grown on Ni foam via a multiscale structural regulation strategy. The introduction of metal doping and defects regulated the morphology of NiBDC for increasing the exposure of electrochemically active sites and adjusted the electronic structure of the Ni active center, which enhanced the OER performance of NiCoBDC-Fc/NF.

Enhanced removal of Cr(VI) from aqueous solutions by polymer-mediated nitrogen-rich reduced graphene oxide.

The efficient removal of heavy metal by rationally designed carbon-based adsorbents is a key challenge in the field of water purification. Herein, we report a nitrogen-enriched lignosulfonate exfoliated graphene oxide (N-LEGO) for hexavalent chromium (Cr(VI)) removal from aqueous solution. The nitrogen content of N-LEGO reached 13.28%, and the ratio of N-bonding configurations (pyri-N:amine-N:pyrro-N:grap-N) was 2.3:1.6:1:2.3. For Cr(VI) with initial concentration of 70 mg L-1 under pH= 2, the residuary concentration after treated by N-LEGO was close to 0.004 mg L-1, which meets the industrial wastewater discharge standard. The Cr(VI) adsorption behavior on N-LEGO can be fitted with the pseudo-second-order kinetics and Freundlich isotherm model well. The adsorption mechanism of Cr(VI) on N-LEGO includes anions electrostatic attraction, reduction and surface chelation. Density functional theory (DFT) simulations showed that N atoms doping was feasible and thermodynamically stable, meanwhile the N-doped system was easier to adsorb Cr2O72- than HCrO4-. The findings of this work can provide a new idea for the development of N-doped carbon-based adsorbents for the removal of highly toxic Cr(VI) from aqueous solutions.

Enhanced removal of toxic hexavalent chromium from aqueous solution by magnetic Zr-MOF@polypyrrole: performance and mechanism.

Magnetic Zr-based metal organic framework (UiO-66) @Polypyrrole (magnetic UiO-66@Ppy) was prepared to eliminate Cr(VI) from water. SEM and TEM results clearly revealed that the magnetic UiO-66@Ppy was a core-double-shell structure with the core of Fe3O4, inner shell UiO-66, and outer shell Ppy. The introduction of zirconium MOFs UiO-66 effectively prevented the agglomeration of polypyrrole and provided more available adsorption sites, the surface area increased from 9.57 m2/g (Ppy) to 10.57 m2/g (Fe3O4@Ppy) and 52.49 m2/g (magnetic UiO-66@Ppy). The magnetic UiO-66@Ppy possessed a high adsorption capacity of 259.1 mg/g in removing Cr(VI) from water. Adsorption kinetics followed the pseudo-second-order model. The removal of Cr(VI) involved the following mechanisms: (1) electrostatic attraction and ions exchange, the HCrO4- was adsorbed on the surface of magnetic UiO-66@Ppy by the protonated N(PpyN+) and Cl-; (2) reduction, Cr(VI) was reduced to Cr(III) by the reductive functional group(-NH-); (3) chelation, Cr(III) was immobilized on adsorbent by amine groups.

Controlling alloy to core-shell structure transformation of Au-Pd icosahedral nanoparticles.

The structure transformation between Au-Pd alloy and core-shell icosahedral nanoparticles was achieved by a one-step aqueous-phase strategy. This strategy provided a way to tune the structure and atomic distribution of Au-Pd icosahedral nanoparticles. It could modulate the electronic structure of Pd, achieving promoted electrocatalytic ability toward the hydrogen evolution reaction.

Functional rGO aerogel as a potential adsorbent for removing hazardous hexavalent chromium: adsorption performance and mechanism.

A novel functional rGO aerogel was synthesized by a facile hydrothermal method. In this process, graphene oxide (GO) was used as the precursor and oxidant to synthesize the aerogels. Ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) and pyrrole monomer (reducing agent) were selected to use as hole scavenger and nitrogen sources. The obtained EDTA-2Na/polypyrrole (Ppy)/rGO aerogel (EPGA) has a high adsorption capacity for Cr(VI) anions, and the maximum adsorption capacity reached 361 mg/g at 298 K at pH of 2. In addition, EPGA exhibited a good ability to selectively remove Cr(VI) anions under the effect of coexisting ions (Cl-, NO3-, SO42-, PO43-, Ni+, Cu2+, Zn2+, and Cd2+) and good regeneration ability. The kinetics process and adsorption isotherm can be fitted well with the pseudo-second-order kinetic model and Freundlich isotherm model, respectively. The removal mechanism involved electrostatic interaction, reduction, ion exchange, and chelation process. This work provides a simple and environmentally friendly synthetic route for EPGA, which will be a potential candidate for efficient removal Cr(VI) anions from industrial wastewater.

Synthesis of nano-scale zero-valent iron-reduced graphene oxide-silica nano-composites for the efficient removal of arsenic from aqueous solutions.

Design and synthesis of arsenic adsorbents with high performance and excellent stability has been still a significant challenge. In this study, we anchored nano-zero-valent iron (NZVI) on the surface of graphene-silica composites (GS) with high specific surface area, forming the NZVI/GS nano-composite. The prepared nano-materials were used to remove As(III) and As(V) through adsorption from aqueous solutions. The results indicated that NZVI particles were dispersed well on the surface of GS, and the NZVI/GS showed great potential to remove As(III) and As(V). Adsorption performance of NZVI/GS for As(III) and As(V) highly depended on the pH of solutions. The experimental data fitted well with the pseudo-second-order kinetic model and the Langmuir isotherm model. The calculated maximum adsorption capacities of NZVI/GS for As(III) and As(V) were up to 45.57 mg/g and 45.12 mg/g at 298 K, respectively, and the adsorption equilibrium could be reached within 60 min. The residual concentrations of As(III) and As(V) after treatment with 0.4 g/L NZVI/GS can meet with the drinking water standard of WHO when the initial concentrations were below 4 mg/L and 3 mg/L, respectively. Moreover, the as-prepared NZVI/GS had excellent anti-interference ability during the process of As removal in the presence of foreign ions. During the As removal process, As(III) was oxidized to As(V), which could be removed through adsorption by electrostatic attraction and complexation. These results indicated that the as-synthesized NZVI/GS composite is a promising adsorbent for the removal of arsenic from aqueous solutions.

[Preparation and Pb2 electrosorption characteristics of MnO2/CFP composite electrode].

The morphological structure and electrochemical properties of the electrode materials have direct impact on the electrosorption results. In this paper, Manganese dioxide ( MnO2) was composed on flexible carbon fiber paper ( CFP) via anodic electrodeposition technique to prepare the MnO2/CFP hybrid electrodes. The electrodes materials prepared showed stable electrochemical property, remarkable electrochemical capacitance, and the specific capacitance reached up to 360 F x g(-1). Electrosorption was conducted with this MnO2/CFP hybrid electrode to treat the waste water with an initial Pb2+ concentration of 6 mg x L(-1), and the effects of deposition time, initial pH, and voltage value on the electrosorption were investigated. It was shown that when the electrodeposition time was 500 s and the application of voltage value was 1.0 V, pH = 5.0, the best electroabsorption result was achieved. After 3 h electrosorption, the residual Pb2+ in the solution was lower than 0.01 mg x L(-1), and the removal efficiency could reach 99%. This study provides a new technology option for the removal of heavy metal ions in low concentrations in the waste water.