Ion Exchange and Antibiofouling Properties of Poly(ether sulfone) Membranes Prepared by the Surface Immobilization of Brønsted Acidic Ionic Liquids via Double-Click Reactions.

Brønsted acidic ionic liquids (BAILs) are unique ionic liquids that display chemical structures similar to zwitterions, and they were typically used as solvents and catalysts. In this work, an imidazole-based BAIL monolayer was fabricated onto poly(ether sulfone) (PES) membranes via surface clicking reactions, and the multifunctionality, including ion exchange and biofouling resistance to proteins and bacteria, was demonstrated, which was believed to be one of few works in which BAIL had been considered to be a novel fouling resistance layer for porous membranes. The successful immobilization of the BAILs onto a membrane surface was confirmed by X-ray photoelectron spectroscopy analysis, contact angle measurement, and ζ potential determination. The results from Raman spectroscopy showed that, as a decisive step prior to zwitterion, the BAIL was deprotonated in aqueous solution, and biofouling resistance to proteins and bacteria was found. However, BAIL displayed ion exchange ability at lower pH, and surface hydrophilicity/hydrophobicity of membranes could be tuned on purpose. Our results have demonstrated that the BAIL grafted onto membranes will not only act as an antibiofouling barrier like zwitterions but also provide a platform for surface chemical tailoring by ion exchange, the property of which will become especially important in acidic solutions where the fouling resistance performances of zwitterions are greatly weakened.

Surface characteristics of a self-polymerized dopamine coating deposited on hydrophobic polymer films.

This study aims to explore the fundamental surface characteristics of polydopamine (pDA)-coated hydrophobic polymer films. A poly(vinylidene fluoride) (PVDF) film was surface modified by dip coating in an aqueous solution of dopamine on the basis of its self-polymerization and strong adhesion feature. The self-polymerization and deposition rates of dopamine on film surfaces increased with increasing temperature as evaluated by both spectroscopic ellipsometry and scanning electronic microscopy (SEM). Changes in the surface morphologies of pDA-coated films as well as the size and shape of pDA particles in the solution were also investigated by SEM, atomic force microscopy (AFM), and transmission electron microscopy (TEM). The surface roughness and surface free energy of pDA-modified films were mainly affected by the reaction temperature and showed only a slight dependence on the reaction time and concentration of the dopamine solution. Additionally, three other typical hydrophobic polymer films of polytetrafluoroethylene (PTFE), poly(ethylene terephthalate) (PET), and polyimide (PI) were also modified by the same procedure. The lyophilicity (liquid affinity) and surface free energy of these polymer films were enhanced significantly after being coated with pDA, as were those of PVDF films. It is indicated that the deposition behavior of pDA is not strongly dependent on the nature of the substrates. This information provides us with not only a better understanding of biologically inspired surface chemistry for pDA coatings but also effective strategies for exploiting the properties of dopamine to create novel functional polymer materials.

Poly (N-vinyl imidazole) gel-filled membrane adsorbers for highly efficient removal of dyes from water.

Energy-efficient and time-saving process for recovery of hazardous dyes from wastewater is highly desired in dyeing industry. In this work, poly(N-vinyl imidazole) (PVI) gel-filled membrane adsorbers were developed for highly efficient recovery of dyes through adsorption filtration. The membrane adsorbers were fabricated via dip-coating of Nylon macroporous membranes in PVI solutions followed by quaternization crosslinking with p-xylylene dichloride (XDC). Physicochemical characterizations indicated that PVI gel was successfully filled and fixed inside the Nylon matrix. In optimized conditions. The treating capacity of membrane adsorbers to typical dye sunset yellow (25 ppm of the feed concentration) reached up to 197 mg/g with the removal ratio >99%. Both the treating capacity and the removal ratio were kept steady even when the permeation flux was as high as 1000 L/m2 h. The membrane adsorbers developed in this work were able to not only remove anionic dyes from water, but also separate anionic dyes from cationic ones. The zeta potential and adsorption tests showed that the electrostatic interaction between PVI gel and dye molecules was responsible for the high removal efficiencies to anionic dyes. The membrane adsorbers can be regenerated effectively with NaOH solution and demonstrated good stability in both acidic and alkaline conditions.

Improved protein-adsorption resistance of polyethersulfone membranes via surface segregation of ultrahigh molecular weight poly(styrene-alt-maleic anhydride).

A styrene-maleic anhydride (SMA) alternating copolymer with ultrahigh molecular weight (M(w)>10(6)) synthesized in super critical carbon dioxide (SC CO(2)) medium was used as hydrophilic polymeric additive in the preparation of polyethersulfone (PES) membranes. The PES/SMA blend membranes were prepared by immersion precipitation process. X-ray photoelectronic spectroscopy (XPS) measurements confirmed that the hydrolyzed SMA preferentially segregated to membrane-coagulant interface during membrane formation. For the PES/SMA blend membranes, no big change was observed in the cross-sectional structure and the mechanical properties were well maintained after SMA addition except that a thicker top layer was formed. The surface morphology analysis by atomic force microscopy (AFM) showed that the membrane surface roughness increased with the added SMA amount. The results of water contact angle, water absorbance measurements and static protein adsorption experiments revealed that the surface enrichment of SMA endowed PES/SMA blend membranes with significantly improved surface hydrophilicity and protein-adsorption resistance.

Surface zwitterionicalization of poly(vinylidene fluoride) membranes from the entrapped reactive core-shell silica nanoparticles.

We demonstrate the preparation and properties of poly(vinylidene fluoride) (PVDF) filtration membranes modified via surface zwitterionicalization mediated by reactive core-shell silica nanoparticles (SiO2 NPs). The organic/inorganic hybrid SiO2 NPs grafted with poly(methyl meth acrylate)-block-poly(2-dimethylaminoethyl methacrylate) copolymer (PMMA-b-PDMAEMA) shell were prepared by surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization and then used as a membrane-making additive of PVDF membranes. The PDMAEMA exposed on membrane surface and pore walls were quaternized into zwitterionic poly(sulfobetaine methacrylate) (PSBMA) using 1,3-propane sultone (1,3-PS) as the quaternization agent. The membrane surface chemistry and morphology were analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. The hydrophilicity, permeability and antifouling ability of the investigated membranes were evaluated in detail. It was found that the PSBMA chains brought highly-hydrophilic and strong fouling resistant characteristics to PVDF membranes due to the powerful hydration of zwitterionic surface. The SiO2 cores and PMMA chains in the hybrid NPs play a role of anchors for the linking of PSBMA chains to membrane surface. Compared to the traditional strategies for membrane hydrophilic modification, the developed method in this work combined the advantages of both blending and surface reaction.

Improving antifouling ability and hemocompatibility of poly(vinylidene fluoride) membranes by polydopamine-mediated ATRP.

The present work aims to improve the antifouling properties and hemocompatibility of poly(vinylidene fluoride) (PVDF) membranes by polydopamine-mediated atom transfer radical polymerization (ATRP). Polydopamine (PDA) was first prepared by the oxidation and self-polymerization in basic aqueous solution. The obtained PDA was used as an additive in the preparation of PVDF membranes via non-solvent induced phase separation (NIPS). Then poly(sulfobetaine methacrylate) (PSBMA), a commonly used zwitterionic polymer, was successfully grafted from the entrapped PDA in membranes through ATRP. The changes in surface morphologies of the PVDF membranes before and after modification were observed by scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Data of water contact angle measurements indicated that the surface hydrophilicity of the modified membranes was remarkably improved compared with that of the pure PVDF membrane. Results of filtration tests revealed that the water permeability and antifouling properties of the PVDF membranes were both increased after modification. Moreover, the hemocompatibility of the modified PVDF membrane was greatly improved due to the incorporation of zwitterionic brushes as demonstrated by in vitro platelet adhesion. Owing to the chemical reactivity of polydopamine as well as its strong interactions with a wide spectrum of solid substrates, this strategy can be extended to other materials and allows the development of novel functional membranes through such a blending process and secondary treatments.

Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive.

Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc.

Route to hemocompatible polyethersulfone membranes via surface aminolysis and heparinization.

Polyethersulfone (PES) membranes with improved hemocompatibility were prepared via solid-liquid interface aminolysis and heparinization. Reactive amino groups were generated by immersing solid PES membranes in proper diamine solution. Heparin was covalent immobilized on the surface via amide bond. The feasibility of surface aminolysis for the introduction of amino groups and the effectiveness for further heparin immobilization were confirmed by surface group analysis. The effect of aminolysis time on surface amino group concentration and bulk mechanical properties was investigated. The surface amino group concentration determined the amount and bioactivity of immobilized heparin chains. SEM images suggested that both the aminolysis and heparinization reaction had little effect on the surface morphology of PES membranes. Contact angle measurement, surface charge analysis, protein and platelet adsorption/adhesion experiment were applied to study the surface properties. The results showed that the heparinized PES membranes displayed enhanced hydrophilicity and hemocompatibility, indicating potential application in blood purification and other blood contacting fields.

Antifouling and antimicrobial polymer membranes based on bioinspired polydopamine and strong hydrogen-bonded poly(N-vinyl pyrrolidone).

A facile and versatile approach for the preparation of antifouling and antimicrobial polymer membranes has been developed on the basis of bioinspired polydopamine (PDA) in this work. It is well-known that a tightly adherent PDA layer can be generated over a wide range of material surfaces through a simple dip-coating process in dopamine aqueous solution. The resulting PDA coating is prone to be further surface-tailored and functionalized via secondary treatments because of its robust reactivity. Herein, a typical hydrophobic polypropylene (PP) porous membrane was first coated with a PDA layer and then further modified by poly(N-vinyl pyrrolidone) (PVP) via multiple hydrogen-bonding interactions between PVP and PDA. Data of water contact angle measurements showed that hydrophilicity and wettability of the membranes were significantly improved after introducing PDA and PVP layers. Both permeation fluxes and antifouling properties of the modified membranes were enhanced as evaluated in oil/water emulsion filtration, protein filtration, and adsorption tests. Furthermore, the modified membranes showed remarkable antimicrobial activity after iodine complexation with the PVP layer. The PVP layer immobilized on the membrane had satisfying long-term stability and durability because of the strong noncovalent forces between PVP and PDA coating. The strategy of material surface modification reported here is substrate-independent, and applicable to a broad range of materials and geometries, which allows effective development of materials with novel functional coatings based on the mussel-inspired surface chemistry.

Hemocompatible and antibacterial porous membranes with heparinized copper hydroxide nanofibers as separation layer.

Here we report the fabrication of a novel heparinized copper hydroxide (Cu(OH)2) nanofiberous membrane with satisfying hemocompatibility and antibacterial properties. The positively charged Cu(OH)2 nanofibers were prepared in a weakly alkaline copper nitrate solution in the presence of 2-aminoethanol. A heparin (Hep) solution was then added dropwise into the solution of nanofibers to immobilize negatively charged heparin onto the Cu(OH)2 nanofibers by electrostatic interaction. A composite Hep@Cu(OH)2 nanofiberous membrane was prepared by filtration and deposition of the heparinized nanofibers onto a polysulfone (PSF) porous membrane. Chemical composition analysis of membrane surface using X-ray photoelectron spectroscopy (XPS) confirmed the successful immobilization of heparin on Cu(OH)2 nanofibers. The amount of immobilized heparin on nanofiberous membrane was determined by a colorimetric assay of toluidine blue dye and the results showed that the amount of immobilized heparin was strongly dependent on the heparin dosage in reaction solution. The results of contact angle measurement indicated that the hydrophilicity of Cu(OH)2 nanofiberous membranes was enhanced by the immobilization of heparin. The adhesion, activation and transmutation of platelets on Hep@Cu(OH)2 membrane were suppressed remarkably due to the introduction of heparin, which suggested that the Hep@Cu(OH)2 membranes had good hemocompatibility. In addition, Cu(OH)2 and Hep@Cu(OH)2 nanofiberous membranes exhibited very good antibacterial activities against Escherichia coli and Staphyloccocus aureus.

Immobilization of bovine serum albumin onto porous polyethylene membranes using strongly attached polydopamine as a spacer.

Based on the self-polymerization and strong adhesion characteristics of dopamine in aqueous solution, a novel and convenient approach was developed to immobilize protein onto porous polyethylene (PE) membranes. A thin polydopamine (pDA) layer was formed and tightly coated onto PE membrane by dipping simply the membrane into dopamine aqueous solution for a period of time. Subsequently, bovine serum albumin (BSA) was bound onto the obtained PE/pDA composite membranes via the coupling between BSA and the reactive polydopamine layer. The firm immobilization of polydopamine layer and BSA was verified by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The results of water contact angle measurement showed that the hydrophilicity of PE membrane was significantly improved after coating polydopamine and binding BSA. The experiments of blood platelet adhesion indicated that BSA-immobilized PE membrane had better blood compatibility than the unmodified PE and the PE/pDA composite membranes. The investigations on hepatocyte cultures and cell viability revealed that the polydopamine coating endowed PE membrane with significantly improved cell compatibility. Compared to BSA surface, polydopamine surface is more favorable for cell adhesion, growth, and proliferation.

Fabrication of superhydrophilic poly(styrene-alt-maleic anhydride)/silica hybrid surfaces on poly(vinylidene fluoride) membranes.

Superhydrophilic organic/inorganic hybrid surfaces have been fabricated on blend membranes of poly(vinylidene fluoride) (PVDF) and poly(styrene-alt-maleic anhydride) (SMA). The blend membranes were prepared from PVDF/SMA mixed solution with N,N-dimethylacetamide (DMAc) as solvent by immersion-precipitation phase inversion process. The gained blend membranes were immersed into γ-aminopropyltriethoxysilane (APTS) solution to generate SMA/silica hybrid surfaces by the reaction between anhydrides and APTS. The hybrid surfaces chemical compositions, morphologies and hydrophilicity were investigated in detail. It demonstrates that the hybrid surfaces possess micro-nano hierarchical structure and display superhydrophilicity property and good stability. Finally, the reaction and formation mechanism of the superhydrophilicity hybrid surface was discussed.

[Membrane fouling control in a free-end comb-like hollow fiber membrane bioreactor].

A free-end comb-like hollow fiber membrane bioreactor was applied to treat wastewater. The results clearly showed that membrane fouling, defined as permeate flux decline, was greatly influenced by membrane module configuration. The permeate flux decline was much less for module b, demonstrating the superiority of module b over module a. Its permeate flux could be maintained in the range of 4.0 to 8.0 L x (m2 x h)(-1) under the operating conditions that temperature was 22-26 degrees C, the mixed liquor suspended solids (MLSS) concentration was 7500-10500 mg/L, aeration intensity was 200 L/h, suction time/ suspended time ratio was 9 min/1 min and suction pressure was 0.02 MPa. As this novel kind of membrane module resulted in high air scouring efficiency, relatively low aeration intensity was needed for the MBR maintenance. In addition, the permeate flux varied a little when suction time/ suspended time ratio changed from 12 min/1 min to 6 min/1 min. The performances of several different cleaning methods were tested and the results indicated that water cleaning + chemical cleaning + ethanol soaking had the best cleaning efficiency. SEM images clearly showed that the membrane surface became cleaner and the membrane holes became more visible after water cleaning + chemical cleaning, compared with water cleaning solely.

Surface modification of PVDF porous membranes via poly(DOPA) coating and heparin immobilization.

Based on the strong adhesive behavior of poly(3,4-dihydroxy-l-phenylalanine) (or poly(DOPA)) on solid surface, poly(vinylidene fluoride) (PVDF) microporous membranes were surface-modified by the self-polymerization of DOPA in aqueous solution. Subsequently, heparin was immobilized covalently onto the obtained PVDF/poly(DOPA) composite membranes by the coupling between heparin and poly(DOPA) coating. The modified membranes were subjected to a long-term washing, and the firm immobilization of poly(DOPA) and heparin was confirmed by X-ray photoelectron spectroscopy (XPS). The results of water contact angle measurements showed that the hydrophilicity of PVDF membranes was significantly improved by the incorporation of poly(DOPA) and heparin. The effects of poly(DOPA) and heparin on membrane surface morphologies were also investigated by scanning electron microscopy (SEM).

Improving hydrophilicity and protein resistance of poly(vinylidene fluoride) membranes by blending with amphiphilic hyperbranched-star polymer.

To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.

[Study on the process for wastewater treatment in submerged rotating membrane bioreactor].

The process for wastewater treatment in submerged rotating membrane bioreactor (SRMBR) was studied. It was found that the effluent COD reduced to 20 mg/L after one day running when the influent COD varied from 160 mg/L to 368 mg/L. The equilibrium membrane flux increased rapidly with increasing rotation speed of membrane in the range of 0 to 25r/min. Within one minute, the increase of suspended suction time could alleviate the membrane fouling. Moreover, higher membrane flux could be reached even at lower aeration/water ratio (15:1) in SRMBR process. The optimum processing condition was suggested as follows: the rotation speed was 25r/min, suction time/suspended time was 9 min/1 min, aeration/water ratio was 15/1, and operation pressure was 25kPa. Under this condition, the equilibrium membrane flux could reach 53.75 L/(m2 x h).

Novel, fluorescent, magnetic, polysaccharide-based microsphere for orientation, tracing, and anticoagulation: preparation and characterization.

A fluorescent, magnetic composite poly(styrene-maleic anhydride) microsphere, suitable for conjugation with polysaccharide, was synthesized using magnetite/europium phthalate particles as seeds by copolymerization of styrene and maleic anhydride. The magnetite/europium phthalate particles were wrapped up by poly(ethylene glycol), which improved the affinity between the seed particles and the monomers. The composite microspheres obtained, with a diameter of 0.15-0.7 microm, contain 586-1013 microg of magnetite/g of microsphere and 0.5-16 mmol surface anhydride groups/g of microsphere. Heparin was conjugated with the reactive surface anhydride groups on the surface of the microspheres by covalent binding to obtain a fluorescent, magnetic, polysaccharide-based microsphere. The microspheres not only retain their bioactivities but also provide magnetic susceptibility and fluorescence. They can be used as a carrier with magnetic orientation and fluorescence tracer for potent drug targeting. The orientation, tracer, and anticoagulation of the fluorescence, magnetic, polysaccharide-based microspheres were studied. The anticoagulant activity of the microspheres and heparin binding capacity reached 54,212.8 U and 607.1 mg/g of dry microspheres. The activity recovery was 50.2%. The anticoagulant activity of the microspheres increases with the increase of the conjugated heparin on the surface of the microspheres and the decrease of the microsphere size. Furthermore, The fluorescent, magnetic, polysaccharide-based microspheres can be easily transported to a given position in a magnetic field and traced via their fluorescence.

[Separation of carbon dioxide from gas mixture by membrane contactor].

In this paper, membrane contactor made of hydrophobic hollow fiber polypropylene porous membrane (HFPPM) was used for separating carbon dioxide (CO2) from CO2/N2 mixtures. The effects of absorbents, concentration and flow rate of feeding gas and absorbent solution, lumen/shell side processes and gas permeability of HFPPM(P) on the CO2 absorption efficiency were investigated. It was found that the absorption efficiency of three absorbents ranged in order of ethanolamine > sodium hydroxide > diethanol amine. For CO2/N2 mixture of c(in) = 20% and v(in) = 0.5-1.0 m3.h-1, and MEA solution of cMEA = 2.5 mol.L-1 and vL = 40-160 L.h-1, the removal efficiencies of CO2 (eta) and the mass transport coefficients (K) was 9.5% - 99.5% and 4.5-6.8 x 10(-4) m.s.-1 respectively. K of the modules made of HFPPM with larger P was relatively larger. eta in lumen process was 30% larger than that in shell process.

[Processing conditions of recirculated MBR for wastewater treatment].

In this paper, wastewater was treated with Recirculated Membrane Bio-Reactor (RMBR) and effluent quality became stable after four days running continuously. Critical membrane flux was increased with increasing crossflow velocity between 0.9-1.9 m/s. Under crossflow velocity of 1.9 m/s, critical membrane flux was enhanced from 72 L/(m2.h) to 76 L/(m2.h) or 81 L/(m2.h) respectively when powdered activated carbon (PAC) or both PAC and alum were added to the system. Between 22 degrees C-30 degrees C, the flux was elevated 1.9% per 1 degree C increased. Fouling materials were removed efficiently through cleaning physically or/and chemically with flux recovery of 47%-94%.