Preparation of superhydrophobic films based on the diblock copolymer P(TFEMA-r-Sty)-b-PCEMA.

The diblock copolymer poly[2,2,2-trifluoroethyl methacrylate-r-styrene]-block-poly[(2-cinnamoyloxyethyl methacrylate)] [P(TFEMA-r-Sty)-b-PCEMA] was synthesized via atom transfer radical polymerization. The copolymer underwent self-assembly in TFEMA/CH2Cl2 to form spherical micelles. Photo-cross-linking of the PCEMA domains of these micelles yielded cross-linked nanoparticles. The cross-linked nanoparticles were subsequently cast from CH2Cl2/methanol solvent mixtures at methanol volume fractions of more than 30% to yield rough surfaces bearing small nanobumps on micron-sized aggregations that were connected together to form cross-linked nanoparticles. These surfaces were superhydrophobic with a water contact angle of 161 ± 1° and a sliding angle of 6 ± 1°. Spraying these nanoparticles onto substrates exhibiting microscale roughness, such as filter paper, by a traditional coating technique also created superhydrophobic surfaces. A thin layer of nanoscale spherical protrusions was observed on the microscale fibers of filter paper by scanning electron microscopy. The coated filter paper samples exhibited a water contact angle and a sliding angle of 153 ± 1° and 9 ± 1°, respectively.

Dialdehyde cellulose (DAC) and polyethyleneimine (PEI) coated polyvinylidene fluoride (PVDF) membrane for simultaneously removing emulsified oils and anionic dyes.

Developing high-efficiency membrane for oil and dye removal is very urgent, because wastewater containing them can cause great damage to human and environment. In this study, a coated membrane was fabricated by applying DAC and PEI onto the commercial PVDF microfiltration membrane for supplying the demand. The coated membrane presents superhydrophlic and superoleophobic properties with a water contact angle of 0o and underwater oil contact angle exceed 150°, as well as excellent low underwater oil adhesion performance. The coated membrane shows high separation efficiency exceeded 99.0% and flux 350.0 L·m-2·h-1 when used for separating for six kinds of oil including pump oil, sunflower oil, n-hexadecane, soybean oil, diesel and kerosene in water emulsions. Additionally, the coated membrane can effectively remove anionic dyes, achieving rejection rates of 94.7%, 93.4%, 92.3%, 90.7% for the CR, MB, RB5, AR66, respectively. More importantly, the membrane was able to simultaneously remove emulsified oil and soluble anionic dyes in wastewater containing both of them. Therefore, this novel coated membrane can be a promising candidate for treating complex wastewater.

Epoxied SiO2 nanoparticles and polyethyleneimine (PEI) coated polyvinylidene fluoride (PVDF) membrane for improved oil water separation, anti-fouling, dye and heavy metal ions removal capabilities.

Epoxied SiO2 nanoparticles and polyethyleneimine (PEI) was used to coating polyvinylidene fluoride (PVDF) membrane for improved anti-fouling, oil water separation, dye and heavy metal ions removal capabilities. Characterization of the modified membrane revealed that the hydrophilic coating layer was applied onto the PVDF substrate successfully. The modified membrane can exhibit a high degree of superhydrophilicity and underwater superoleophobicity. Consequently over 98% of the oil was retained when this membrane was used in oil water separation. The hydrophilic coating layer enhanced the membrane antifouling performance, and its flux recovery rate reached 96.3% after filtration and washing with bovine serum protein solution (BSA). In addition, the modified membrane presented the ability to adsorb organic dyes and heavy metal ions in water and reject them via filtration. Most importantly, the crosslinking reaction between the epoxied SiO2 nanoparticles and PEI imparts a high degree of stability to the coating layer. Thanks to the simple fabrication method and multifunctional performances of the coating layer described in this report, it may be used to modify other substrates.

Hydrophilic and Positively Charged Polyvinylidene Fluoride Membranes for Water Treatment with Excellent Anti-Oil and Anti-Biocontamination Properties.

Membrane fouling limits the rapid development of membrane separations. In this study, a blend membrane containing polycationic liquid (P(BVImBr1-co-PEGMA1)) is presented that can improve the antifouling performance of polyvinylidene fluoride (PVDF) membranes. By mixing the polycationic liquid into PVDF, an improved membrane-surface hydrophilicity and enlarged membrane porosity were detected. The water contact angle decreased from 82° to 67°, the porosity enlarged from 7.22% to 89.74%, and the pure water flux improved from 0 to 631.68 L m-2 h-1. The blend membrane surfaces were found to be always positively charged at pH 3~10. By applying the membranes to the filtration of oil/water emulsion and bovine serum albumin (BSA) solution, they showed a very high rejection rate to pollutants in wastewater (99.4% to oil droplets and 85.6% to BSA). The positive membrane surface charge and the increased membrane hydrophilicity resulted in excellent antifouling performance, with the flux recovery rates of the dynamic filtration tests reaching 97.3% and 95.5%, respectively. Moreover, the blend membranes demonstrated very low BSA adhesion and could even kill S. aureus, showing excellent antifouling properties.

Visible-light-driven 3D Bi5O7I/BiOCl microsphere with enhanced photocatalytic capability: Performance, degradation pathway, antibacterium and mechanism.

It is well known that both of the separation efficiency of photogenerated carriers and the response capability to visible light remarkably affect the photocatalytic performance. In the present work, a 3D microsphere of Bi5O7I/BiOCl heterojunction catalyst was synthetised. The synergy of Bi5O7I and BiOCl not only significantly enhances the transfer rate and separation efficiency of carriers, but also heightens light absorption capacity. As-prepared Bi5O7I/BiOCl (40 wt% BiOCl) has a higher degradation efficiency on doxycycline hydrochloride (DC) (90 min, 83.0%) and super high inhibition rate (90 min, 99.92%) on Escherichia coli under visible light, compared to the two monomers. Pollutants DC is finally decomposed into CO2, H2O and small molecule intermediates by generated h+, •OH and •O2-. The effects of reactive radicals follow the order of •OH radicals > h+ radicals ≫ •O2- and e- radicals. The possible structures of intermediates and four possible degradation pathways involved were also discussed. In addition, As-synthetised Bi5O7I/BiOCl has preferable reusability and excellent chemical stability. Biological toxicity experiments also verify that Bi5O7I/BiOCl is a green and environmentally friendly composite material. This strategy provides a green, low-toxic way for the application of traditional type II heterojunction in the fields of environmental remediation and photocatalysis.

Preparation of Multipurpose Polyvinylidene Fluoride Membranes via a Spray-Coating Strategy Using Waterborne Polymers.

As reported herein, the waterborne polymers poly(glycidyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) P(GMA-co-mPEGMA) and polyethyleneimine (PEI) were used to prepare multipurpose polyvinylidene fluoride (PVDF) membranes via a direct spray-coating method. P(GMA-co-mPEGMA) and PEI were alternately sprayed onto the PVDF membrane to yield stable cross-linked copolymer coatings. The successful coating of polymers onto the membrane surface was verified by scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy characterization. The coated membrane exhibited oil rejection rates that exceeded 99.0% for oil water mixture separation and 98.0% for oil/water emulsion separation. The flux recovery ratio reached 96.7% after bovine serum albumin filtration and washing with water. The removal efficiencies of the coated membrane M3 for Congo red, methyl orange, methylene blue, and crystal violet, Pb(II), Cu(II), and Cd(II) were 82.4, 83.9, 6.3, 26.8, 90.6, 91.3, and 86.2%, respectively. Thus, it can be used for the removal of dyes and heavy metal ions from wastewater. The antibacterial activities of the coated membranes were also confirmed by the inhibition zone tests and confocal laser scanning microscopy analysis. In addition, the cross-linking strategy provides the coated membranes with excellent durability and repeatability. More importantly, the use of water as the solvent can ensure that the application of these membrane coatings proceeds via a very safe and environmentally friendly coating process.

Smart Self-Cleaning Membrane via the Blending of an Upper Critical Solution Temperature Diblock Copolymer with PVDF.

Poly(2,2,2-trifluoroethyl methacrylate)-b-poly(imidazoled glycidyl methacrylate-co-diethylene glycol methyl ether methacrylate) (PTFEMA-b-P(iGMA-co-MEO2MA)) containing an upper critical solution temperature (UCST) polymer chain was prepared and blended with poly(vinylidene fluoride) (PVDF) to produce a thermoresponsive membrane with smart self-cleaning performance. The successful preparation of the membrane was demonstrated by attenuated total reflection-Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy characterization. The membrane shows UCST performance, and its flux changes with the filtrate temperature as the UCST polymer chain stretches out and contracts in response to various temperatures. In addition, the UCST polymer chain can disrupt the foulant and push it away from the membrane when the temperature is above the UCST and thus enables membranes to exhibit a smart self-cleaning behavior. To the best of our knowledge, this work is the first report of a smart self-cleaning membrane based on the blending of a diblock copolymer containing a UCST polymer chain with PVDF.

Molecular Understanding and Design of Porous Polyurethane Hydrogels with Ultralow-Oil-Adhesion for Oil-Water Separation.

Materials with opposite affinities toward oil and water have been extensively used to coat porous substrates for oil-water separation, but the applications of these materials have been limited by the need for complex coating processes as well as the short-term adherence of these materials onto different substrates under extreme conditions. As reported herein, the robust porous polyurethane hydrogel has been theoretically and structurally designed with ultralow-oil-adhesion properties which is free stand without depending on additional substrates. The combination of superhydrophilic properties along with the underwater superoleophobic behavior of this porous hydrogel allows gravity driven separations of oil-water mixtures, and its antiadhesion performance toward oil prevents undesirable oily fouling. The underwater superoleophobic properties were also illustrated by molecular dynamics simulation to understand the resisting effect of hydrated layers. The as-prepared porous hydrogel shows ultrahigh oil-water separation efficiencies of 99.9% for various oil-water mixtures, ranging from those containing viscous oils (pump oil and peanut oil) to organic solvents (n-hexane, n-hexadecane, and toluene). In addition, this hydrogel is durable even with exposure to various harsh conditions including acidic and basic media (pH 0-14) as well as exposure to mechanical abrasion. We believe that the combination of facile preparation, substrate independence, gravity driven separation, antifouling properties, high durability, as well as the outstanding separation flux and efficiency of this robust porous hydrogel will help to advance the design and application of materials in oil-water separation fields.

Nanobodies Based on a Sandwich Immunoassay for the Detection of Staphylococcal Enterotoxin B Free from Interference by Protein A.

As one of the leading causes of food poisoning, staphylococcal enterotoxins (SEs) secreted by Staphylococcus aureus pose a serious threat to human health. The immunoassay has become the dominant tool used for the rapid detection of harmful bacteria and toxins as a result of its excellent specificity. However, with regard to SEs, staphylococcal protein A (SpA) is likely to bind with the fragment crystallizable (Fc) terminal of the traditional antibody and result in a false positive, limiting the practical application of this method. Therefore, to eliminate the bottleneck problem, the sandwich immunoassay was development by replacing the traditional antibody with a nanobody (Nb) that lacked a Fc terminal. Using 0.5 × 107 colony-forming units, the Nb library was constructed using Bactrian camels immunized with staphylococcal enterotoxin B (SEB) to obtain a paired Nb against SEB with good affinity. A sandwich enzyme-linked immunosorbent assay (ELISA) was developed using one Nb as the capture antibody and a phage-displayed Nb with signal-amplifying properties as the detection antibody. In optimal conditions, the current immunoassay displayed a broad quantitative range from 1 to 512 ng/mL and a 0.3 ng/mL limit of detection. The recovery of spiked milk, milk powder, cheese, and beef ranged from 87.66 to 114.2%. The Nbs-ELISA was not influenced by SpA during the detection of SEB in S. aureus food poisoning. Therefore, the Nb developed here presented the perfect candidates for immunoassay application during SE determination as a result of the complete absence of SpA interference.

Enhancing the Antifouling Properties of Poly(vinylidene fluoride) (PVDF) Membrane through a Novel Blending and Surface-Grafting Modification Approach.

In this study, poly(vinylidene fluoride) (PVDF) membrane was modified through a novel approach by first blending an active component (poly(vinylidene fluoride-co-chlorotrifluoroethylene), P(VDF-co-CTFE)) with the PVDF base material, followed by surface grafting of the membrane on the active component to obtain a triblock copolymer functional structure. The prepared membranes were characterized by various analyses, including Fourier-transform infrared, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscope, and filtration tests. It was found that the modified membrane surface showed a much better hydrophilicity (water contact angle of 67.3°) and oleophobicity (oil contact angle of 129.7°). The modification reduced the average surface pore size (from 0.1495 to 0.1072 µm) and thus lowered the pure water flux (from 364.0 to 224.6 L m-2 h-1 at 0.10 MPa of transmembrane pressure), but significantly increased the relative flux recovery (RFR) and the retention efficiency of the modified membrane during the filtration of bovine serum albumin solution and oil/water emulsion. For example, the modified membranes showed 98.6% oil retention (at feed concentration of 0.4 g L-1), 92.7% RFR by simple water flushing after filtration, and a consistently high oil removal of 96% or above during a five-cycle-continuous filtration test, as compared to 30.4% oil retention and 51.8% RFR for unmodified PVDF/P(VDF-co-CTFE) blend membrane.

Preparation, physicochemical characterization and application of acetylated lotus rhizome starches.

Acetylated lotus rhizome starches were prepared, physicochemically characterized and used as food additives in puddings. The percentage content of the acetyl groups and degree of substitution increased linearly with the amount of acetic anhydride used. The introduction of acetyl groups was confirmed via Fourier transform infrared (FT-IR) spectroscopy. The values of the pasting parameters were lower for acetylated starch than for native starch. Acetylation was found to increase the light transmittance (%), the freeze-thaw stability, the swelling power and the solubility of the starch. Sensorial scores for puddings prepared using native and acetylated lotus rhizome starches as food additives indicated that puddings produced from the modified starches with superior properties over those prepared from native starch.

Amylose-directed synthesis of CuS composite nanowires and microspheres.

Reported are the synthesis and characterization of CuS composite nanowires and microspheres in the presence of amylose. The preparation involved first the complexation of amylose with Cu(2+) of CuCl(2) at 70°C. Cu(2+) complexation was confirmed by a conductivity reduction of CuCl(2) after amylose addition. Also, the aggregation state of the amylose changed after Cu(2+) as revealed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). At the Cu(2+) to α-D-glucopyranosyl unit molar ratio r of 0.70 and 1.41, the amylose aggregated into microspheres that were approximately 150 and 250 nm in diameter. Adding sodium thiosulfate resulted in the production of an amorphous precipitate consisting presumably of CuS(2)O(3). At r=0.70 and 1.41, CuS(2)O(3) precipitated inside the template of Cu(2+)/amylose microspheres as nanoparticles, while a twisted nanowire-like structure was produced at r=0.92. CuS(2)O(3) decomposed under heating at 100 °C to yield crystalline CuS nanoparticles.

Superhydrophobic hierarchically assembled films of diblock copolymer hollow nanospheres and nanotubes.

Reported are the formation of rough particulate films from cross-linked diblock copolymer vesicles and nanotubes and the wetting properties of the resultant films. The diblock copolymers used were F66M200 and F95A135, where the subscripts denote the repeat unit numbers, whereas M, A, and F denote poly(2-cinnamoyloxyethyl methacrylate), poly(2-cinnamoyloxyethyl acrylate), and poly(2,2,2-trifluoroethyl methacrylate), respectively. The precursory polymers to F66M200 and F95A135 were prepared by atom transfer radical polymerization. In 2,2,2-trifluoroethyl methacrylate (FEMA), a selective solvent for F, vesicles and tubular micelles were prepared from F66M200 and F95A135, respectively. Photo-cross-linking the M and A blocks of these aggregates yielded hollow nanospheres and nanotubes bearing F coronal chains. These particles were dispersed into CH2Cl2/methanol, where CH2Cl2 was a good solvent for both blocks and methanol was a poor solvent for F. Casting CH2Cl2/methanol dispersions of these particles yielded films consisting of hierarchically assembled diblock copolymer nanoparticles. For example, the hollow nanospheres fused into microspheres bearing nanobumps after being cast from CH2Cl2/methanol at methanol volume fractions of 30 and 50%. The roughness of these films increased as the methanol volume fraction increased. The films that were cast at high methanol contents were superhydrophobic, possessing water contact angles of ∼160° and water sliding angles of ∼3°.

Robust superamphiphobic coatings based on silica particles bearing bifunctional random copolymers.

Reported herein is the growth of bifunctional random copolymer chains from silica particles through a "grafting from" approach and the use of these copolymer-bearing particles to fabricate superamphiphobic coatings. The silica particles had a diameter of 90 ± 7 nm and were prepared through a modified Stöber process before atom transfer radical polymerization (ATRP) initiators were introduced onto their surfaces. Bifunctional copolymer chains bearing low-surface-free-energy fluorinated units and sol-gel-forming units were then grafted from these silica particles by surface-initiated ATRP. Perfluorooctyl ethyl acrylate (FOEA) and 3-(triisopropyloxy)silylpropyl methacrylate (IPSMA) were respectively used as fluorinated and sol-gel-forming monomers in this reaction. Hydrolyzing the IPSMA units in the presence of an acid catalyst yielded silica particles that were adorned with silanol-bearing copolymer chains. Coatings were prepared by spraying these hydrolyzed silica particles onto glass and cotton substrates. A series of four different copolymer-functionalized silica particles samples bearing copolymers with similar FOEA molar fractions (fF) of ~80% but with different copolymer grafting mass ratios (gm) that ranged between 12.3 wt% and 58.8 wt%, relative to silica, were prepared by varying the polymerization protocols. These copolymer-bearing silica particles with a gm exceeding 34.1 wt% were used to coat glass and cotton substrates, yielding superamphiphobic surfaces. More importantly, these particulate-based coatings were robust and resistant to solvent extraction and NaOH etching thanks to the self-cross-linking of the copolymer chains and their covalent attachment to the substrates.