Constructing green superhydrophilic and superoleophobic COFs-MOFs hybrid-based membrane for efficiently emulsion separation and synchronous removal of microplastics, dyes, and pesticides.

Oil spills and micropollutants have become thorny environmental issues, posing serious threat to ecosystem and human health. To settle such dilemma, this study successfully constructed a robust and environmentally-friendly MOFs-COFs hybrid-based membrane (FS-50/COF(MATPA)-MOF(Zr)/PDA@PVDF) for the first time through solution synthesis and solvothermal method, combined with surface modification of FS-50 molecule. Importantly, we employed a simple two-step strategy to obtain the high-aspect-ratio MOFs fibers: (1) solvent regulation to generate smaller needle-like whiskers during the in-situ growth of MOFs on COFs; (2) high pressure induced directional crystallization in filtration process. The introduction of polydopamine (PDA) greatly improved the adhesion between coating and PVDF membrane. The in-situ growth of high length-diameter ratio MOFs fibers on blocky COFs greatly enhanced the specific surface area of MOFs-COFs hybrid, thus provided sufficient absorption sites. The functional groups of FS-50 endowed the hybrid membrane with superhydrophilicity and superoleophobicity, which facilitated to selectively penetrate water molecules and repel non-polar pollutants. The separation efficiency and decontamination mechanism of hybrid membrane to the simulated oily wastewater (containing various MPs, dyes, and pesticides) were investigated through experiments and theoretical calculations. The hybrid membrane could selectively and synchronously adsorb various dyes (20 mg/L-120 mg/L, almost 100% removal) and pesticides (10 mg/L for DIF and TET, adsorption rates 93.2% and 90.9%, respectively) from oil-water emulsion (50 mL). The large-scale coated sponge (6 cm × 4.5 cm × 3 cm) could quickly achieve separation of oil-water mixture (almost 100%) with a water permeability of more than 162 L m-2·h-1·bar-1, and simultaneously remove various MPs (PP-2000, PP-100, PE-2000, PS-100, 0.2 g/300 mL for each), Sudan Ⅲ (C0 = 200 mg/L), and DIF (C0 = 10 mg/L) from a simulant oily wastewater (300 mL), with the removal rates of almost 100% for MPs, 99.7% for Sudan Ⅲ, and 95.8% for DIF. Furthermore, we elucidated the removal mechanism of pesticide and dyes through simulating the theoretical adsorption energy and potential adsorption sites. The hybrid membrane not only provides a promising candidate for the removal of multiple pollutants from oil-water emulsion, but also opens a new strategy for achieving efficient and clean aquatic environment restoration.

Fabrication of a cycloalkyl-monolith for on-line solid-phase extraction and determination of four polyphyllins in plasma.

A cycloalkyl-based polymer monolithic column for solid-phase extraction was prepared via radical polymerization using cyclohexyl methacrylate as the monomer. The preparative conditions such as crosslinker/monomer ratio and the amount of the porogens were optimized and the resulting monoliths were characterized by scanning electron microscopy and nitrogen adsorption-desorption method. On-line solid-phase extraction-high-performance liquid chromatography was performed to quantitatively analyse polyphyllin I, II, VI and VII contained in herbal medicine of paridis rhizome in mouse plasma using the homemade optimized monolithic SPE column combined with a C18 column, in which water was used to remove the plasma matrix while the polyphyllins in the mouse plasma were eluted by acetonitrile-water (42:58, V/V). Results obtained from the method validation show that the present method is feasible for the quantitative analysis of the four polyphyllins in plasma. The developed method was further applied for the real mouse plasma sample. These results show that the homemade cycloalkyl-based polymer monolithic SPE column has good ability for clean-up of the interfering bio-matrix and simultaneously extracting the four polyphyllins from mouse plasma. Furthermore, the present method is a promising method for quantitative determination of saponins compounds from complex bio-samples with the advantages of simple and efficient.

Engineering green MOF-based superhydrophobic sponge for efficiently synchronous removal of microplastics and pesticides from high-salinity water.

Microplastics (MPs) and pesticides are becoming an intractable environmental issue due to their wide spreading and non-degradable nature, posing serious threat to ecosystem and human health. To settle such dilemma, this work reasonably designed a superhydrophobic MOF-based coated sponge (ODSOSS/TiO2/Ni-MOF/PDA@Sponge) through the combination of an environmentally friendly in-situ supersaturated coprecipitation and polysesiloxane modification method. Among them, (I) the introduction of polydopamine (PDA) not only improves the adhesion between coatings and sponge, but also enhances the growth of MOF structure through complexation. (II) The obtained Ni-MOF shows large-area microscale anthemy structure with multilayered flaky texture, forming heterogeneously hierarchical structure with the deposited TiO2 nanoparticles, which promotes photodegradation ability of TiO2 owing to great specific surface area of Ni-MOF. (III) The high specific large area Ni-MOF supplies sufficient action sites for linkage of PDA and polysesiloxane molecules with unique nanocage-like structure, thus further greatly increasing adsorption force for various pollutants. (IV) The superhydrophobicity protect the porous channels of MOF from contamination of various absorbed pollutants, while TiO2 nanoparticles effectively photodegrade the absorbed organic pollutants, endowing the sponge superior recyclability. The superhydrophobic sponge selectively rapidly and synchronously adsorbs various MPs (maintained almost 100% after 60 cycles) and pesticides (adsorption rates 71.6%-95.1%) from high-salinity water. The large-area sponge (9 cm × 6 cm × 1 cm) simultaneously removes almost 100% MPs (40 mg/L), Sudan Ⅲ (10 mg/L), kerosene (30 mL/L), and four pesticides (10 mg/L) within 1 min. Particularly, four pesticides are quickly photocatalytic degraded by the coated sponge. The free radical capture trials show that hydroxyl radicals (·OH) are the main active species of pesticide degradation. Furthermore, we reveal the negative centers where pesticide molecules are most vulnerable to ·OH attack, on basis of the charge distribution and molecular electrostatic potential (MEP) analysis. The adsorption mechanisms are carefully clarified through theoretical calculation and experimental data. This work not only provide an effective superhydrophobic candidate for MPs and pesticides removal in a broad applicable scope (especially in high-salinity wastewater), but also opens a new strategy for environmental remediation.

Mechanically durable anti-bacteria non-fluorinated superhydrophobic sponge for highly efficient and fast microplastic and oil removal.

Microplastics (MPs) pollution evolves into a global environmental problem to be solved urgently. Although many studies are exploring ways to remove MPs from water environment, most of them are lack of selectivity and low efficiency. Herein, considering the fascinating absorption selectivity of superwetting materials, a robust magnetic-responsive superhydrophobic and superoleophilic sponge was firstly used to quickly eliminate MPs from water with very high efficiency. The functional sponge was fabricated by a non-fluorinated coating technique that consisted of polydimethylsiloxane (PDMS) grafted Fe3O4 particle, PDMS grafted halloysite nanotubes, and PDMS binder. The coated sponge achieved excellent mechanically durable and chemically stable superhydrophobicity that resisted a series of severe treatments. It was unquestionable to show very fast oil absorption. What's more, it especially showed very high adsorption capacity (24.3-48.2 mg/g) and could quickly adsorb almost 100% MPs (polypropylene, polyvinyl chloride, and polyethylene) from aqueous suspensions. Moreover, the removal rates remained almost 100% for these MPs after 50 cycles. Besides, the coated sponge had excellent salt tolerance and antibacterial activity to Escherichia coli (E. coli) (99.91%) and Staphylococcus aureus (S. aureus) (90.46%). The adsorption mechanism of the coating was discussed from the perspectives of molecular structure, electronic effect, steric hindrance, and size-scale effect. The absorption driving force mainly derived from the intra-particle diffusion under capillary attraction, whilst slight electrostatic interaction, hydrogen bond interaction, and σ-p (or p-p) conjugation between PDMS and MPs. This functional sponge was destined to be a new strategy in the removal of MPs and other solid pollutants, especially in the high-salinity and rich-microorganism water environment.

Enhanced cellular uptake and tumor penetration of nanoparticles by imprinting the "hidden" part of membrane receptors for targeted drug delivery.

The widely existing transmembrane helices can serve as a novel type of binding site for recognizing corresponding membrane receptors. Through imprinting the transmembrane domain of certain receptors, here we report the construction of polymeric nanoparticles which can achieve enhanced cellular uptake and permeability in target tissues for tumor-targeted drug delivery.

Flow and fracture behavior of aluminum alloy 6082-T6 at different tensile strain rates and triaxialities.

This study aims to investigate the flow and fracture behavior of aluminum alloy 6082-T6 (AA6082-T6) at different strain rates and triaxialities. Two groups of Charpy impact tests were carried out to further investigate its dynamic impact fracture property. A series of tensile tests and numerical simulations based on finite element analysis (FEA) were performed. Experimental data on smooth specimens under various strain rates ranging from 0.0001~3400 s-1 shows that AA6082-T6 is rather insensitive to strain rates in general. However, clear rate sensitivity was observed in the range of 0.001~1 s-1 while such a characteristic is counteracted by the adiabatic heating of specimens under high strain rates. A Johnson-Cook constitutive model was proposed based on tensile tests at different strain rates. In this study, the average stress triaxiality and equivalent plastic strain at facture obtained from numerical simulations were used for the calibration of J-C fracture model. Both of the J-C constitutive model and fracture model were employed in numerical simulations and the results was compared with experimental results. The calibrated J-C fracture model exhibits higher accuracy than the J-C fracture model obtained by the common method in predicting the fracture behavior of AA6082-T6. Finally, the Scanning Electron Microscope (SEM) of fractured specimens with different initial stress triaxialities were analyzed. The magnified fractographs indicate that high initial stress triaxiality likely results in dimple fracture.

[Analysis and separation of organic and inorganic speciations of soluble zinc in edible flowers].

Considering the medicinal effects of the edible flowers, the authors studied the separation of trace element zinc's soluble organic and inorganic speciations in water decoction of three edible flowers: Chrysanthemum, Cottonrose hibiscus and Honeysucker by using the 0.45 microm membrane filter and amberlite XAD-2 macroreticular resins. And trace element zinc contents were determined by atomic absorption spectrometry. The optimal conditions for separation had been established. This study verifies the economic value of developing edible flowers, and provides theoretical basis for developing edible flowers as the third functional food materials.