Boosting Demulsification and Antifouling Capacity of Membranes via an Enhanced Piezoelectric Effect for Sustaining Emulsion Separation.

Traditional superwettable membranes for demulsification of oil/water emulsions could not maintain their separation performance for long because of low demulsification capacity and surface fouling during practical applications. A charging membrane could repel the contaminants for a while, the charge of which would gradually be neutralized during the separation progress. Here, a superhydrophilic piezoelectric membrane (SPM) with sustained demulsification and antifouling capacity is proposed for achieving prolonged emulsion separation, which is capable of converting inherent pulse hydraulic filtration pressure into pulse voltage. A pulse voltage up to -7.6 V is generated to intercept the oil by expediting the deformation and coalescence of emulsified oil droplets, realizing the demulsification. Furthermore, it repels negatively charged oil droplets, avoiding membrane fouling. Additionally, any organic foulants adhering to the membrane undergo degradation facilitated by the generated reactive oxygen species. The separation data demonstrate a 98.85% efficiency with a flux decline ratio below 14% during a 2 h separation duration and a nearly 100% flux recovery of SPM. This research opens new avenues in membrane separation, environmental remediation, etc.

Manipulation of Heterogeneous Surface Electric Potential Promotes Osteogenesis by Strengthening RGD Peptide Binding and Cellular Mechanosensing.

The heterogeneity of extracellular matrix (ECM) topology, stiffness, and architecture is a key factor modulating cellular behavior and osteogenesis. However, the effects of heterogeneous ECM electric potential at the micro- and nanoscale on osteogenesis remain to be elucidated. Here, the heterogeneous distribution of surface potential is established by incorporating ferroelectric BaTiO3 nanofibers (BTNF) into poly(vinylidene fluoridetrifluoroethylene) (P(VDF-TrFE)) matrix based on phase-field and first-principles simulation. By optimizing the aspect ratios of BTNF fillers, the anisotropic distribution of surface potential on BTNF/P(VDF-TrFE) nanocomposite membranes can be achieved by strong spontaneous electric polarization of BTNF fillers. These results indicate that heterogeneous surface potential distribution leads to a meshwork pattern of fibronectin (FN) aggregation, which increased FN-III7-10 (FN fragment) focal flexibility and anchor points as predicted by molecular dynamics simulation. Furthermore, integrin clustering, focal adhesion formation, cell spreading, and adhesion are enhanced sequentially. Increased traction of actin fibers amplifies mechanotransduction by promoting nuclear translocation of YAP/Runx2, which enhances osteogenesis in vitro and bone regeneration in vivo. The work thus provides fundamental insights into the biological effects of surface potential heterogeneity at the micro- and nanoscale on osteogenesis, and also develops a new strategy to optimize the performance of electroactive biomaterials for tissue regenerative therapies.

Designing Robust Superhydrophobic Materials for Inhibiting Nucleation of Clathrate Hydrates by Imitating Glass Sponges.

Superhydrophobic surfaces are suggested to deal with hydrate blockage because they can greatly reduce adhesion with the formed hydrates. However, they may promote the formation of fresh hydrate nuclei by inducing an orderly arrangement of water molecules, further aggravating hydrate blockage and meanwhile suffering from their fragile surfaces. Here, inspired by glass sponges, we report a robust anti-hydrate-nucleation superhydrophobic three-dimensional (3D) porous skeleton, perfectly resolving the conflict between inhibiting hydrate nucleation and superhydrophobicity. The high specific area of the 3D porous skeleton ensures an increase in terminal hydroxyl (inhibitory groups) content without damaging the superhydrophobicity, achieving the inhibition to fresh hydrates and antiadhesion to formed hydrates. Molecular dynamics simulation results indicate that terminal hydroxyls on a superhydrophobic surface can inhibit the formation of hydrate cages by disordering the arrangement of water molecules. And experimental data prove that the induction time of hydrate formation was prolonged by 84.4% and the hydrate adhesive force was reduced by 98.7%. Furthermore, this porous skeleton still maintains excellent inhibition and antiadhesion properties even after erosion for 4 h at 1500 rpm. Therefore, this research paves the way toward developing novel materials applied in the oil and gas industry, carbon capture and storage, etc.

A superwetting stainless steel mesh with Janus surface charges for efficient emulsion separation.

Design of charged materials for demulsification of ionic surfactant-stabilized oil-in-water emulsions is emerging in recent years. Herein, a superwetting stainless steel mesh with Janus surface charges (Janus SSM) was prepared by respectively brush-coating polyethyleneimine/aminated carbon nanotubes (PEI/CNTs-NH2) coating and polyacrylic acid (PAA) coating on its two sides. Two demulsification mechanisms, i.e., electrostatic attraction-repulsion and electrostatic repulsion-attraction based on the synergism of two oppositely charged sides were proposed. Combined with the superwettability and optimized pore size, the Janus SSM can successfully be used to demulsify, coalesce and separate emulsions. In detail, the Janus SSM exhibited separation efficiencies of up to 99.29%, 97.12% for SDS- and DTAC-stabilized oil-in-water emulsions respectively under the electrostatic attraction-repulsion mechanism, and up to 97.10%, 98.57% under the electrostatic repulsion-attraction mechanism. The results indicated that the electrostatic attraction-repulsion mechanism proposed in this study is conductive to achieving higher efficiency in emulsion separation. Furthermore, excellent durability extend the operation life of Janus SSM. This Janus SSM, which combines opposite charges on its two sides, may advance the development of charged materials for emulsion separation.

Molecular design and experimental study of cellulose conversion to 5-hydroxymethylfurfural catalyzed by different ratios of Brønsted/Lewis acid ionic liquids.

Cellulose conversion into 5-hydroxymethylfurfural (5-HMF) is difficult because of the strong hydrogen bonding existed in cellulose chains. Brønsted/Lewis (B/L) biacidic functionalized ionic liquids (ILs) have great advantages in acid-catalyzed tandem reactions, but the catalytic effect of ILs differs considerably depending on B/L acid ratios. Therefore, this work designed a series of reactions with different proportions of biacidic ILs for the preparation of 5-HMF from cellulose. The tandem reaction is often performed in the presence of a solvent, and the activity of the catalyst is also affected by the solvent. Therefore, in this work, the solvation model density(SMD) model was introduced into the quantum chemical calculation method for molecular design to predict the catalytic effect and explore the catalytic mechanism. The calculation results and experiments jointly showed that [(HSO3-P)2im]Cl·ZnCl2 had the highest efficiency, with a 5-HMF yield of 65.66%. This study facilitates the directional optimization design of the catalyst.

Toxicological effects of atenolol and venlafaxine on zebrafish tissues: Bioaccumulation, DNA hypomethylation, and molecular mechanism.

The beta-blocker atenolol (ATE), and the selective serotonin and norepinephrine reuptake inhibitor, venlafaxine (VEN) are frequently detected in municipal wastewater effluents, but little is known about their ecotoxicological effect on aquatic animals. Herein, ATE and VEN were selected to explore their accumulation and global DNA methylation (GDM) in zebrafish tissues after a 30-day exposure. Molecular dynamics (MD) stimulation was used to investigate the toxic mechanism of ATE and VEN exposure. The results demonstrated that ATE and VEN could reduce the condition factor of zebrafish. The bioaccumulation capacity for ATE and VEN was in the order of liver > gut > gill > brain and liver > gut > brain > gill, respectively. After a 30-day recovery, ATE and VEN could still be detected in zebrafish tissues when exposure concentrations were ≥10 µg/L. Moreover, ATE and VEN induced global DNA hypomethylation in different tissues with a dose-dependent manner and their main target tissues were liver and brain. When the exposure concentrations of ATE and VEN were increased to 100 µg/L, the global DNA hypomethylation of liver and brain were reduced to 27% and 18%, respectively. In the same tissue exposed to the same concentration, DNA hypomethylation induced by VEN was more serious than that of ATE. After a 30-day recovery, the global DNA hypomethylations caused by the two drugs were still persistent, and the recovery of VEN was slower than that of ATE. The MD simulation results showed that both ATE and VEN could reduce the catalytic activity of DNA Methyltransferase 1 (DNMT1), while the effect of VEN on the 3D conformational changes of the DNMT1 domain was more significant, resulting in a lower DNA methylation rate. The current study shed new light on the toxic mechanism and potential adverse impacts of ATE and VEN on zebrafish, providing essential information to the further ecotoxicological risk assessment of these drugs in the aquatic environment.

A novel Janus sponge fabricated by a green strategy for simultaneous separation of oil/water emulsions and dye contaminants.

A novel Janus sponge with the ability to remove complex contaminants from water is reported. Firstly, a superhydrophilic sponge (PA@PEI-sponge) is prepared via synthesizing negatively charged phytic acid@polyethyleneimine (PA@PEI) nanoparticles and assembling them on the surface of polydopamine (PDA) and PEI-modified polyurethane (PU) sponge through electrostatic adsorption. The Janus sponge is generated by modifying one side of the PA@PEI-sponge with PDMS, which exhibits superior separation efficiency and high filtration flux toward both water-in-oil and oil-in-water emulsions due to its multiplex selective wettability and the interconnected and tortuous 3D porous channels. The numerous negatively charged active sites of PA@PEI nanoparticles and PDA layer impart the superhydrophilic PA@PEI-sponge with the removal efficiency of 39.95 ± 0.27% for malachite green (MG) via simple flow-through filtration, which can be improved to 99.92 ± 0.07% by Janus modification. More importantly, the Janus sponge exhibits an excellent treatment capacity for complex mixtures containing emulsified oil and dye, with the separation efficiency above 99.59%. The Janus sponge also demonstrates the effective separation of real industrial wastewater collected from an acrylic dyeing plant. Together with a facile and green preparation strategy, this Janus sponge shows excellent application potential for simultaneous dye removal and oil/water emulsion separation.

Janus sand filter with excellent demulsification ability in separation of surfactant-stabilized oil/water emulsions: An experimental and molecular dynamics simulation study.

Developing efficient separation materials for surfactant-stabilized oil/water emulsions is of great importance while significantly challenging. In this work, a sand filter with Janus channels was prepared by simply mixing superhydrophilic and superhydrophobic quartz sand in a mass ratio of 1:1. Due to the imbalanced force of droplets in those Janus channels, better separation performance under gravity was achieved for both surfactant-stabilized oil-in-water and water-in-oil emulsions than the superhydrophilic or superhydrophobic sand filter alone. It also received high flux (1080.13 L m-2 h-1 for dichloroethane-in-water emulsion and 1378.07 L m-2 h-1 for water-in-dichloroethane emulsion) and high separation efficiency (99.80% for dichloroethane-in-water emulsion and 99.98% for water-in-dichloroethane emulsion). Molecular dynamics based computational work and experimental studies revealed that the Janus channels of mixed sand layer exhibited greater interaction energy with emulsion droplets for more efficient adsorption, resulting in better demulsification capability and separation performance. The as-prepared Janus sand filters retained excellent separation performance after 50 cycles of the stability test. Together with the needs on only cheap and easily accessible raw materials and its environmentally friendly preparation method, this Janus sand filtration process exhibits its great potential for the separation of surfactant-stabilized oil/water emulsions.

Enhanced Movement of Two-Component Droplets on a Wedge-Shaped Ag/Cu Surface by a Wettability Gradient.

The wedge-shaped Ag/Cu surface with a contact angle (CA) [droplet of 30 vol % propylene glycol (PG)] of 18.6° in the wedge track and 64.6° at its periphery was fabricated through a facile gradient displacement reaction on the Cu substrate. The aqueous droplet of 30% PG could realize directed motion on the wedge track without back-end pinning, moving in a two-stage process of front-end spreading and subsequent back-end shrinking. A wettability gradient from 64.6 to 18.6° on the wedge surface could enhance the droplet motion, especially during the second stage. A favorable length of the wettability gradient (15 mm) was obtained, capable of moving the droplet the farthest displacement of 21.6 mm at a velocity of 0.53 mm/s on a wedge track with the wedge angle of α = 10° and length of 25 mm. The driving force arising from the wettability gradient during the second stage was evaluated theoretically to elucidate the effect of the length of the wettability gradient on the movement. Finally, three T-shaped self-driven surface micromixers composed of a mixing zone with uniform wettability and a transportation zone with different gradients were designed to test the drainage ability of droplets away from the surface. The wedge track combined with the wettability gradient was found to be capable of removing the mixed droplet completely out of the mixing region and flowing away, while the droplet would attach or stay in the mixing zone if actuated by the shape gradient or the wettability gradient alone.

Metformin-Induced Epigenetic Toxicity in Zebrafish: Experimental and Molecular Dynamics Simulation Studies.

The increased detection of many prescription drugs in aquatic environments has heightened concerns of their potential ecotoxicological effects. In this study, the effects of metformin (MEF) exposure on tissue accumulation, gene expression, and global DNA methylation (GDM) in zebrafish were investigated. The toxic mechanism of MEF exposure was simulated by molecular dynamics (MD) to reveal any conformational changes to DNA methyltransferase 1 (DNMT1). The results showed MEF accumulation in the gills, gut, and liver of zebrafish after 30 days of exposure, and the bioaccumulation capacity was in the order of gut > liver > gills. After a 30 day recovery period, MEF could still be detected in zebrafish tissues in groups exposed to MEF concentrations ≥ 10 µg/L. Moreover, the liver was the main site of GDM, and the restoration of GDM in the liver was slower than that in the gut and gills during the recovery period. Furthermore, MEF could induce the abnormal expression of CYP3A65, GSTM1, p53, and DNMT1 genes in the liver due to the formation of hydrogen bonds between MEF and the protein residues of those genes. The MD simulation allowed for the mechanistic determination of MEF-induced three-dimensional (3D) conformational changes and changes to the catalytic activity of DNMT1.

Fabrication of superhydrophilic PVDF membranes by one-step modification with eco-friendly phytic acid and polyethyleneimine complex for oil-in-water emulsions separation.

Superhydrophilic membranes with simultaneous underwater superoleophobicity are highly desirable and worth exploring for separation of emulsified oil from water. In this work, combining the strong negative charges of phytic acid (PA) and the high cationic charge density of polyethyleneimine (PEI), an eco-friendly PA@PEI polyelectrolyte complex was synthetized in aqueous solution. And then the polyelectrolyte complex was deposited onto hydrophobic PVDF membranes through a one-step assembly approach with high convenience, endowing the membranes with superhydrophilic and underwater superoleophobic property. The as-prepared PA@PEI/PVDF membrane shows outstanding static and dynamic water stability, and was successfully used to separate multiple oil-in-water emulsions, with an average rejection rate exceeding 98.5% and a water flux up to 12203.6 L m-2∙h-1∙bar-1. Furthermore, the water flux can be recovered to a high level after four separation-washing cycles, showing excellent antifouling performance and recovery capability. Together with its natural raw materials and environmentally friendly preparation strategy, the PA@PEI/PVDF membrane shows great potential in practical treatment of emulsified oily wastewater.

A durable superwetting clusters-inlayed mesh with high efficiency and flux for emulsion separation.

How to rapidly and efficiently separate surfactant-stabilized emulsions has been a great challenge for oil/water separation materials. In this work, a durable superwetting copper mesh with high efficiency and flux for gravity-driven emulsion separation was fabricated by subtly inlaying polydopamine/polyethyleneimine@aminated carbon nanotubes (PDA/PEI@CNTs-NH2) clusters in the mesh pores. The porous clusters with abundant cationic groups render the mesh with superwettability, submicron permeation channels and positive charges, so as to achieve strong demulsification ability. Based on the superwettability and the strong demulsification ability, the PDA/PEI@CNTs-NH2 clusters-inlayed copper mesh (PPC-CM) exhibited high separation efficiency of over 99.5% for various anionic surfactant-stabilized oil-in-water emulsions. Meanwhile, the permeation flux of PPC-CM solely driven by gravity is as high as 3946.3 L m-2 h-1. The strong demulsification ability and high permeation flux of the superwetting mesh are due to the synergistic action of charge-screening effect of -NH3+ and size-sieving effect of optimized pore size. Furthermore, the resultant mesh exhibited excellent durability that it could resist serious physical abrasion and chemical corrosion. Especially the mesh after repeated separation can recover its positive charge by a simple acid treatment. These excellent performances highlight the superwetting mesh a promising potential for sustainable separation of highly stabilized oil/water emulsions.

Facile fabrication of an F-POSS polymer-based liquid-repellent Cu mesh with excellent durability and self-cleaning performance.

A facile method that combines alkali-assisted oxidation and -SH chelation with a click chemistry reaction was employed to create an F-POSS polymer surface (fluorinated octavinyl polyhedral oligomeric silsesquioxane polymer)-based Cu mesh (F-POSS-OM). The as-prepared F-POSS-OM surface displayed a cohering hierarchical nano-F-POSS polymer granule/micro-Cu(OH)2 wire structure, which provided a re-entrant geometry needed for liquid-repellency and low liquid sliding angles (<15°). Moreover, the easy-prepared structure endows the F-POSS-OM with remarkable durability for mechanical and chemical damages, including wear abrasion, tape-peeling, 100 cm-height hammer impact, severe hand twisting, strong acid/base/salt solutions, and high temperatures. Importantly, F-POSS-OM still retained excellent self-cleaning performance even after being subjected to these damages.

Allylated chitosan-poly(N-isopropylacrylamide) hydrogel based on a functionalized double network for controlled drug release.

Smart hydrogels with dual network were presented since a new allylated chitosan was conceived. As a double network hydrogel, its first network consisted of poly(N-isopropylacrylamide) worked as the gel matrix, and its second network with Schiff base bond enabled itself function as a molecular switch through the formation and break of the bond. When only the intestinal fluid was used, the second network could provide efficient protection for the loaded drug, and the drug release mechanism conformed to the non-Fickian type diffusion. While pre-treated with simulated gastric fluid, the switch would be opened and the mechanism was the Fickian type, which increased the cumulative percentage of drug release by about 25% and the release time by about 300 min. Besides, the hydrogel was characterized by 1H NMR, FT-IR and SEM. The effects of allylated chitosan, pH and crosslinker on the swelling ratio and morphology of hydrogel were also studied.

Ca2+, redox, and thermoresponsive supramolecular hydrogel with programmed quadruple shape memory effect.

A new shape memory hydrogel, which can be programmed with quadruple geometries when stimuli are applied sequentially, is presented. With a new redox-responsive stimulus coupled with two other common regulation mechanisms, this hydrogel shows multiple shape memory behaviours, which is promising for various applications, especially drug delivery.

Synthesis and self-assembly behavior of polyhedral oligomeric silsesquioxane-based triblock copolymers in selective solvents by dissipative particle dynamics simulation.

A polyhedral oligomeric silsesquioxane (POSS)-based hybrid triblock copolymer - methyl methacrylate-b-perfluoroalkylethyl methacrylate-b-methacrylisobutyl polyhedral oligomeric silsesquioxane (PMMA-b-PFMA-b-PMAPOSS) was synthesized via an atom transfer radical polymerization (ATRP) method. The self-assembly behavior of triblock copolymers in selective solvents of tetrahydrofuran (THF) and trichlorotrifluoroethane (F113) was studied using dissipative particle dynamics (DPD) simulation. The effects of the block sequence and volume ratio of F113/THF were discussed. The aggregate morphology and size were also characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The simulation results showed that the spherical micelle with core-shell-corona or core-mixed shell structure could be formed and the micelle size increased with the F113 content, which was in qualitative agreement with the experimental results. The DPD simulation revealed the dynamic process of the formation of aggregates at the mesoscopic scale, which can be considered as an adjunct to experiments and provides other valuable information for the experiments.

NiMn2O4 as an efficient cathode catalyst for rechargeable lithium-air batteries.

NiMn2O4 with different crystal structures was successfully synthesized and evaluated as a cathode catalyst for rechargeable Li-air batteries for the first time. The result reveals that the intermediate spinel structure between normal and inverse spinels demonstrates faster kinetics towards ORR/OER than the normal spinel, leading to a better battery performance.

Droplet Motion on a Shape Gradient Surface.

We demonstrate a facile method to induce water droplet motion on an wedge-shaped superhydrophobic copper surface combining with a poly(dimethylsiloxane) (PDMS) oil layer on it. The unbalanced interfacial tension from the shape gradient offers the actuating force. The superhydrophobicity critically eliminates the droplet contact line pinning and the slippery PDMS oil layer lubricates the droplet motion, which makes the droplet move easily. The maximum velocity and furthest position of droplet motion were recorded and found to be influenced by the gradient angle. The mechanism of droplet motion on the shape gradient surface is systematically discussed, and the theoretical model analysis is well matched with the experimental results.

Inspired by Stenocara Beetles: From Water Collection to High-Efficiency Water-in-Oil Emulsion Separation.

Inspired by the water-collecting mechanism of the Stenocara beetle's back structure, we prepared a superhydrophilic bumps-superhydrophobic/superoleophilic stainless steel mesh (SBS-SSM) filter via a facile and environmentally friendly method. Specifically, hydrophilic silica microparticles are assembled on the as-cleaned stainless steel mesh surface, followed by further spin-coating with a fluoropolymer/SiO2 nanoparticle solution. On the special surface of SBS-SSM, attributed to the steep surface energy gradient, the superhydrophilic bumps (hydrophilic silica microparticles) are able to capture emulsified water droplets and collect water from the emulsion even when their size is smaller than the pore size of the stainless steel mesh. The oil portion of the water-in-oil emulsion therefore permeates through pores of the superhydrophobic/superoleophilic mesh coating freely and gets purified. We demonstrated an oil recovery purity up to 99.95 wt % for surfactant-stabilized water-in-oil emulsions on the biomimetic SBS-SSM filter, which is superior to that of the traditional superhydrophobic/superoleophilic stainless steel mesh (S-SSM) filter lacking the superhydrophilic bump structure. Together with a facile and environmentally friendly coating strategy, this tool shows great application potential for water-in-oil emulsion separation and oil purification.

Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction.

A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst.