Thin-Film Nanocomposite Membranes with Nature-Inspired MOFs Incorporated for Removing Fluoroquinolone Antibiotics.

A nanofiltration membrane functionalized with metal-organic frameworks (MOFs) is promising to enhance micropollutant removal and realize wastewater reclamation. However, the current MOF-based nanofiltration membranes still suffer from severe fouling problems with an indefinable mechanism when used for antibiotic wastewater treatment. Hence, we report a nature-inspired MOF-based thin-film nanocomposite (TFN-CU) membrane to explore its rejection and antifouling behavior. Compared with unmodified membranes, the optimal TFN-CU5 membrane (with 5 mg·mL-1 C-UiO-66-NH2) had high water permeance (17.66 ± 1.19 L·m-2·h-1·bar-1), exceptional rejection for norfloxacin (97.92 ± 2.28%) and ofloxacin (95.36 ± 1.03%), and excellent long-term stability for treating synthetic secondary effluent with antibiotic rejection over 90%. Furthermore, it also showed superior antifouling capability (flux recovery up to 95.86 ± 1.28%) in bovine serum albumin (BSA) filtration after fouling cycles. Deriving from the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) approach, the antifouling mechanism between BSA and the TFN-CU5 membrane was mainly attributed to the inhibited adhesion forces because the growing short-ranged acid-base interaction caused repulsive interfacial interactions. It is further revealed that BSA fouling behavior is slightly retarded under an alkaline environment, while strengthened in the presence of calcium ions and humic acid, as well as high ionic strength. In short, the nature-inspired MOF-based TFN membranes possess exceptional rejection and organic fouling resistance, giving insights into the design of antifouling membranes during antibiotic wastewater reclamation.

Cross-Linked and Doped Graphene Oxide Membranes with Excellent Antifouling Capacity for Rejection of Antibiotics and Salts.

Graphene oxide (GO) membranes have suffered from the instability of water permeability and low rejection of pollutant separation. In this paper, a reasonable modification protocol for GO nanosheets at the molecular level was proposed. A molecular cross-linking strategy was adopted to regulate the interlayer spacing of GO nanosheets, and nanofiltration membranes with high water stability and excellent antifouling capacity were prepared, which could effectively reject antibiotics and salts. The GO1-MPD0.5 (the mass ratio of GO nanosheets to MPD is 1:0.5) and GO/GO1-MPD0.5-0.25 (the doping ratio of GO1-MPD0.5 is 25%) membranes had stable water permeability of 4.22 ± 0.06 and 3.65 ± 0.11 L m-2 h-1 bar-1, and the rejection rates for ciprofloxacin (CIP) and ofloxacin (OFX) were 93.35 ± 3.62 and 95.48 ± 2.97 and 85.89 ± 6.52 and 88.21 ± 3.67%, respectively. Molecular dynamics simulations well explained the high water stability of membranes, and the cross-linked hydrophobic benzene ring played a role in the rejection of pollutant molecules. Moreover, the GO1-MPD0.5 membrane showed excellent antifouling capacity and the flux recovery ratio (FRR) was more than 98%. This paper provides a new idea for the design of nanofiltration membranes with high stability and good rejection permeability at the molecular level and provides a prospect for the application of nanofiltration membranes in practical water treatment and water purification.

Double-charged self-assembled rGO/g-C3N4 membrane prepared by "functional group substitution" for heavy metal ions rejection at low pressure.

Heavy metals are still the critical pollutants in industrial wastewater and there is an urgent need for efficient and environmentally friendly treatment technologies. Reduced graphene oxide (rGO) is widely used for preparations of nanofiltration (NF) membranes but suffers from poor hydrophilicity and electronegativity. In this work, a double-charged rGO/g-C3N4-P membrane was prepared for removal of heavy metals at low pressure. Graphitic carbon nitride (g-C3N4) assisted reduction of GO membranes under ultraviolet (UV) irradiation, and the modification of functional groups with high polarity improved the hydrophilicity of membrane surface. The filtration performance for heavy metals of rGO/g-C3N4-P membrane was evaluated under low pressure (1-2 bar). The rejection rates of Cu2+, Cr3+, Mn2+, Cd2+, and Pb2+ by membranes reduced by UV for 18 h (rGO/g-C3N4-18-P membrane) reached 94.72 %, 98.05 %, 82.32 %, 88.2 % and 77.15 %, respectively. In the experiment of mixed simulated wastewater, the rejection rates of NO3- and SO42- both reached >95 %. Outstanding rejection rates were attributed to the interaction and the synergy effect of double-charged layers as well as steric effects. Meanwhile, the water flux of rGO/g-C3N4-18-P membrane was as high as 37.14-50.16 L m-2h-1bar-1 (1-2 bar). The high flux was due to the reduced degree of oxidation so that water molecules transported between GO nanochannels more smoothly and the transport path was shortened through the nanopores of g-C3N4. Obviously, flux and heavy metal rejection of rGO/g-C3N4-18-P membrane were simultaneously improved, breaking "trade-off" effect. Furthermore, rGO/g-C3N4-18-P membrane showed excellent antifouling ability and the potential for heavy metal wastewater filtration in comparison with other NF membranes reported in literature.

Magnetic Three-Phase Single-Drop Microextraction for Rapid Amplification of the Signals of DNA and MicroRNA Analysis.

The detection of nucleic acids usually suffers from a lengthy amplification process. To obtain an enhanced signal within several seconds, a magnetic three-phase single-drop microextraction (MTP-SDME) approach was developed for the quantification of nucleic acids. First, a target-triggered recycling amplification strategy was used to constitute magnetic branched DNA/Fe3O4 networks, which displayed peroxidase-like catalytic activity toward the 3,3',5,5'-tetramethylbenzidine colorimetric reaction. The networks were separated and enriched by rapid (6 s) MTP-SDME (with only 6 µL of solvent required), thereby producing highly sensitive signals for the quantification of nucleic acids. The signals were significantly amplified by the triple strategy (network formation, MTP-SDME, and catalytic reaction). The application of magnetic extraction minimized the background signal, avoided sample matrix effects, and enhanced the analyte signals. This assay achieved linear calibration curves of between 0.5 aM and 1 pM for microRNA-122 (miRNA-122) and between 1 aM and 1 pM for HBV-T (a DNA fragment from hepatitis B virus). Limits of detection of 0.15 aM for miRNA-122 and 0.34 aM for HBV-T were attained, with relative standard deviations of <5.0% (n = 3). Furthermore, the procedure was applied to determine miRNA-122 and HBV-T in genuine serum samples from hepatocellular carcinoma patients.