The safety and efficacy of low molecular weight dextran (LMWD) in pharmaceutical applications critically depend on the uniformity of its molecular weight distribution. In this study, a novel ultrafiltration (UF) modified membrane was prepared by UV-induced surface graft polymerization on the commercial polysulfone (PSf) membrane for the efficient separation of LMWD. Benzophenone (BP) was employed as the photoinitiator to initiate the grafting polymerization of the difunctional monomer divinylbenzene (DVB). During the polymerization process, DVB underwent both chain homopolymerization and intermolecular crosslinking, forming a dense three-dimensional network that significantly reduced the membrane pore size and enhanced its separation selectivity. The optimized PSf-g-DVB membrane, prepared with a concentration of 2 wt% DVB and 1 wt% BP, achieved over 85% rejection of 20 kDa dextran, while the rejection rate for 2 kDa dextran was only 0.2 %, with a water permeance of 5.4 L m- 2 h- 1 & sdot;bar- 1. Furthermore, the membrane demonstrated excellent stability, maintaining a rejection difference of 70% between the two different molecular weights of dextrans after 48 h of continuous filtration. In filtration experiments with mixed dextran solutions, the PSf-g-DVB membrane exhibited a separation factor as high as 11.5, nearly 9 times higher than that of the commercial PSf membrane, further confirming the feasibility of UV-grafted membrane modification for the selective sieving of LMWD, and offering a green and effective approach for pharmaceutical-grade dextran purification.
Anionic organic fouling of rigid anion-exchange membranes (AEMs) limits electrodialysis (ED) for treating highsalinity organic wastewater, particularly in streams containing aromatic surfactants. Here, a poly(sodium 4-styrenesulfonate) (PSS) interlayer is constructed on a BPPO-based AEM via a homogeneous spray-coating strategy, where PSS is blended into the casting solution and co-deposited onto the same substrate membrane. The sprayed layer forms a continuous, defect-free coating without observable delamination, while the ion-exchange capacity, water uptake, swelling ratio, surface resistance, and limiting current density remain essentially unchanged. Fouling tests using sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS) (50-150 mg & sdot;L-1, 10-30 mA & sdot;cm-2) show that, although the transmembrane voltages of pristine and PSS-modified membranes are broadly comparable, the PSS-modified membranes exhibit substantially lower post-fouling area resistance; in SDBS solutions, the resistance increase is attenuated by up to two orders of magnitude. Scanning electron microscopy, optical observation, and molecular dynamics simulations consistently indicate that the PSS-enriched interlayer suppresses compact deposit build-up and limits foulant penetration into the membrane phase. This work provides a simple and scalable approach to mitigate anionic organic fouling on rigid AEMs.
Fully aromatic fluorinated polyamide nanofiltration membranes are manifesting the great potential in organic solvent nanofiltration (OSN) especially for their excellent structural stability when exposed to solvents and enhanced nonpolar organic solvent permeance compared with the conventional polyamide membranes. However, the fluorinated amino monomers are difficult to be dissolved in water that impedes the large-scale manufacture of fluorinated polyamide selective layers via the typical interfacial polymerization at the wateralkane interfaces. Herein, we report a straightforward and effective strategy for fabricating aromatic fluorinated polyamide nanofiltration membranes at gas/liquid interfaces while hydrophobic 2,2-bis(4-aminophenyl) hexafluoropropane gases and trimesoyl chloride solutions are selected as the gas and liquid phases, respectively. The obtained membranes show outstanding hydrophobicity with water contact angles of 92 degrees, which is beneficial for the nonpolar organic solvent permeance. The molecular dynamics simulations could also prove that the fluorine-containing groups exhibit much lower absolute interaction energies with the nonpolar solvents compared with those of polar ones. Therefore, our membranes demonstrate an extremely high n-hexane permeance of 21.52 L m-2 h-1 & sdot;bar-1 while maintaining a low MWCO of approximately 452 Da. Moreover, the high fluorine contents endow the membranes with good stability resulting in almost unchanged rejection and permeance during long-term operation.
When an aqueous salt solution permeates through a nanofiltration (NF) membrane, a permeate with a different pH from that of the feed is obtained. The underlying mechanism for the pH change accompanied by ion rejection is not fully understood. In particular, systematic studies have not been performed on using NF membranes to treat aqueous solutions of multivalent ions. Consequently, we conducted NF experiments on aqueous solutions of KCl, K2SO4 and MgCl2 with different concentrations (2 – 900 mEq L−1) and pHs (3 – 10). We employed the Donnan steric pore model with dielectric exclusion (DSPM-DE) to quantify the ion rejection and pH change. The trends for the ion rejection and pH change depended strongly on the salt species. The experimentally determined ion rejection and pH change under various test conditions were effectively analyzed by using the DSPM-DE model. The permeate pH was determined by the membrane charge as well as the size and valence of the ion species. Important insights were gained into how ion rejection and pH changes are affected by the feed solution composition and the charge, dielectric, and structural properties of the membrane, even for systems containing divalent cations or anions.
Gas permeability and plasma leakage resistance are key performance requirements for hollow fiber membranes (HFMs) in extracorporeal membrane oxygenation (ECMO), yet they are typically constrained by an inherent structural trade-off. In this study, PP/SiO2 hollow fiber mixed matrix membranes (HF MMMs) were prepared through a hybrid induced phase separation (HIPS) approach, in which oleic acid (OA) and Rhodiasolv® PolarClean (PL) were employed as a dual-diluent system. By incorporating hydrophobic SiO2 nanoparticles into the casting system, the membrane formation process was simultaneously regulated at both the phase separation and crystallization stages. The introduced SiO2 nanoparticles promoted earlier liquid-liquid phase separation and accelerated PP crystallization via heterogeneous nucleation, thereby driving the membrane morphology from a mixed cellular/bicontinuous structure toward a highly interconnected bicontinuous architecture with a thinner dense outer layer and higher porosity. This synergistic structural evolution significantly enhanced gas transport while maintaining excellent plasma leakage resistance. The optimized membrane containing 3 wt% SiO2 achieved an N2 flux of 5.33 ± 0.07 mL min−1·cm−2·bar−1, a porosity of 47%, and a plasma leakage resistance time of 9900 min. Compared with commercial PP and PMP oxygenation membranes, the developed membrane exhibited a superior balance between gas permeation and plasma leakage resistance. Moreover, it also showed improved hemocompatibility, as evidenced by prolonged intrinsic coagulation time and reduced platelet loss. This work demonstrates that hydrophobic SiO2 is an effective additive for engineering PP oxygenation membranes with simultaneously enhanced gas transport, prolonged plasma leakage resistance, and favorable blood compatibility, providing a promising strategy for advanced ECMO membrane design.
In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully"green"and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.
Plasma leakage and thrombosis remain critical challenges limiting the long-term performance of poly(4-methyl-1-pentene) (PMP) hollow fiber membranes (HFMs) in extracorporeal membrane oxygenation (ECMO). In this work, a hierarchical hydrophobic modification strategy was developed to construct a stable anti-wetting interface on PMP HFMs. Surface hydroxyl groups were first generated via Fenton-induced oxidation, followed by interfacial coupling with trimesoyl chloride (TMC). Subsequently, SiO2 nanoparticles were grafted to create a micro/nano-structured rough surface, and further modified with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17-FAS) to reduce surface energy. Under the optimized conditions (120 min Fenton pre-treatment, 60 min TMC reaction, and 0.1% (mass) SiO2 nanoparticles), the modified PMP–SiO2/17-FAS membrane exhibited a high N2 flux of 54.1 ml·cm–2·min–1·MPa–1, while the plasma leakage resistance time was significantly prolonged from 5910 to 8775 min. In addition, bovine serum albumin adsorption was reduced by approximately 50%, indicating enhanced antifouling performance. Coagulation tests further revealed a selective prolongation of activated partial thromboplastin time, while prothrombin time, thrombin time, and international normalized ratio remained nearly unchanged, suggesting suppressed contact-induced coagulation activation without disturbing normal coagulation pathways. The enhanced performance could be attributed to the synergistic effect of micro/nano-structured roughness and the fluorinated low-surface-energy layer, which stabilizes a non-wetting interfacial state and reduces protein-surface interactions. This work provides a feasible strategy for simultaneously improving plasma leakage resistance and hemocompatibility of PMP-based oxygenation membranes.
The surfaces of polyamide-based low-pressure reverse osmosis (RO) membranes were modified with poly(2-methoxyethyl acrylate) (PMEA) via surface-initiated atom transfer radical polymerization for the first time to achieve low-fouling characteristics. The successful grafting of PMEA was demonstrated by attenuated total reflectance Fourier-transform infrared spectroscopy and zeta potential measurements. The grafting amount could be tuned from 0.020 to 0.23 mg cm-2 by changing the grafting time. The modified membranes maintained their salt rejection performances with slight reductions of pure water permeability especially when the grafting amount was smaller than 0.05 mg cm-2. This result indicated that the grafted PMEA had almost no effect on salt rejection but slightly increased the permeation resistance. Compared with unmodified membranes, the modified membranes were found to exhibit low fouling against a variety of organic substances, such as lysozyme, guar gum and tetraethylene glycol monooctyl ether. The results indicate that surface modification of a low-pressure RO membrane with PMEA is a feasible method to obtain a membrane with low-fouling characteristics.
The rapid and complex dynamics of interfacial polymerization (IP) have long hindered real-time monitoring, limiting fundamental insights into the synthesis-structure-performance relationship of polyamide thin-film composite (PA TFC) membranes. In this work, the IP process, where aqueous and organic monomers react to form a thin PA membrane layer, was successfully simulated using the Dissipative Particle Dynamics (DPD) method at a large scale, with the hexane-trimesoyl chloride/water-piperazine (hexane-TMC/water-PIP) system serving as a representative model. Coarse-grained models and interaction parameters for all molecular species were first developed, and a DPD-based protocol for simulating the IP reaction was subsequently established, enabling a systematic investigation of membrane formation at the mesoscale level. By adopting the concentrations employed in experimental studies, the simulation results showed that, in the early stage of IP, highmolecular-weight polymer chains form rapidly; as steric hindrance accumulates, shorter chains are increasingly generated, stabilizing the PA molecular weight. Then, the effect of monomer concentration on membrane formation dynamics and the resulting PA layer morphology was systematically investigated. The results showed that simultaneous increases in both monomer phases promote the formation of shorter PA chain segments, leading to increased membrane thickness and reduced pore size. In contrast, increasing the concentration of a single monomer phase favors the formation of longer PA chains, resulting in negligible changes in membrane thickness while slightly reducing pore size. Finally, a support-free IP process was employed to prepare PA membranes, and the corresponding membrane structures and thickness evolution were measured to validate the simulation results. This work aims to provide a large-scale, DPD-based model capable of simulating the IP process in different practical systems to form TFC membranes, thereby enabling a deeper understanding of membrane formation kinetics.
This study first evaluates the potential of amorphous silica membranes for separating hydrofluorocarbons (HFCs). The ideal selectivity of HFC-32 (difluoromethane) to HFC-125 (pentafluoroethane) through dimethoxydiphenylsilane-derived silica membranes was as high as 329 at 200 degrees C, over ten times higher than previous polymer-based membranes. The membranes were prepared via chemical vapor deposition at 600 degrees C, and the effects of temperature (25-200 degrees C) and pressure (0.2-0.6 MPa) on permeance were measured. HFC-32 permeance was in the range of 10-8 mol m-2 s-1 Pa-1, increasing with temperature, while HFC-125 permeance remained around 10-11 mol m-2 s-1 Pa-1 and was largely temperature independent. The permeances of both the gases showed no pressure dependence. These results highlight that higher temperatures are advantageous, a novel finding from this study. Considering the permeation characteristics of H2, N2, and SF6 as well, the permeations of HFC-32 and HFC-125 appear to be governed by the molecular-sieving mechanism.
From the perspective of sustainable development, the loose nanofiltration (NF) membrane with high permeability and exceptional separation capabilities for dye/salt mixtures has become increasingly appealing to treating dyeing wastewater. This study presents a novel polysulfone (PSf) loose NF membrane with a gradient structure, prepared via a one-step hybrid induced phase separation (HIPS) method without post-treatment. The sulfolane (SFL) was firstly selected as the diluent for PSf and an asymmetric cross-section structure comprising a bi-continuous main body and thin skin layer could be induced due to the mass transfer between SFL and the coagulation (cold water) during the HIPS process. Then, the pore size of the membrane surface was able to be decreased by using PEG400 as an additive. The results demonstrated that when PSf and PEG400 concentrations were 20 and 2.5 wt%, respectively, the optimized PSf loose NF membrane exhibited a significantly higher pure water permeability (49.53 L/(m(2)hbar)) and a superior rejection of 99.3 % for a small molecular dye (EBT) while letting >90 % of the salts of NaCl and Na2SO4 to permeate. The optimized PSf loose NF membranes displayed stable high dye rejection and a good permeability effect on NaCl during long-term stability testing. Moreover, this study provides a fundamental framework for developing loose NF asymmetric membranes to remove dyes from salt wastewater.
The high-salinity wastewater generated by the textile industry presents a substantial challenge in the effective separation of dyes and inorganic salts, particularly concerning cationic dyes, which pose severe environmental pollution risks. Leveraging the combined effects of size exclusion and electrostatic repulsion, positively charged and loose nanofiltration (LNF) membranes have demonstrated the capability to efficiently reject cationic dyes while ensuring high permeance of inorganic salts. Herein, a new type of positively charged LNF membrane was prepared with trimethylamine (TMA) nucleophilic substitution reaction on the 4-Vinylbenzyl chlorostyrene (VBC)/polysulfone (PSf) chloride-grafted (TMA/VBC-g-PSf) membranes. VBC, a highly reactive small molecule featuring two functional groups (active vinyl (CH2=CH-) and benzyl chloride (C-Cl)), was stably anchored onto the surface of PSf ultrafiltration (UF) membranes via vinyl groups. Furthermore, the C-Cl was nucleophilically replaced by the tertammonium group of TMA, forming a quaternary ammonium layer. Thereby, an ultra-thin positively charged selective layer with micro-convex structure was formed onto the PSf membrane surface, endowing the LNF membrane with ultra permeance and high Na2SO4/Victoria blue B (VB) selectivity. The optimized M-2 membrane, with 0.5 wt% VBC and 30 wt% TMA grafting concentration, yielded both high levels of pure water permeance (186.42 L center dot m-2 center dot h-1 center dot bar-1) and an excellent Na2SO4/VB selectivity of 497.5 (high VB rejection of 99.8 % compared to low Na2SO4 rejection of 0.5 %). After 16 h of continuous operation, the separation efficiency of the M-2 membrane for both mixed solution and single-component solution remained consistent and stable, demonstrating its feasibility and high potential in the field of inorganic salts/cationic dyes separation. This study offers valuable insights into innovative methodologies for the production of LNF membranes tailored for dye wastewater treatment.
Organic fouling is one of the primary factors limiting the long-term stability of electro-driven membrane systems (EDMS). This review synthesizes evidence on over 60 identified organic-foulants, including organic acids, surfactants, pharmaceuticals, proteins, polysaccharides, and polymers, organizing and evaluating foulants based on molecular size, charge, and cleanability. Systematic comparison reveals that low-molecular-weight and aromatic species penetrate deeply and cause irreversible fouling, while macromolecular and colloidal organics form removable surface layers. We assess trade-offs between aromatic and aliphatic backbones, the role of side-chain functionalities in tuning interfacial affinity, and diverse surface-engineering strategies that enhance resistance to organic fouling. Beyond phenomenological observations, the review highlights multilevel mitigation strategies encompassing pretreatment, electrodialysis reversal, high-frequency pulsing, surface modification, and intelligent cleaning design. In conclusion, while organic fouling remains an inherent challenge, this review confirms that its effects are controllable through integrated material and process strategies, ultimately upholding the central tenet of “Organic-Fouling Inevitable, Control Achievable” and laying the groundwork for next-generation anti-organic-fouling EDMS.
We have developed novel hydrogen-selective silica membranes by counter-diffusion chemical vapor deposition (CVD) of trimethylmethoxysilane (TMMOS), as a silica precursor, with oxygen. Through systematically varying the CVD conditions, especially the concentration of the TMMOS vapor, the duration of the CVD reaction, and the flow rate of N2 for supplying the TMMOS vapor, we determined that the optimal preparation conditions are 0.81-0.94 mol m-3, 60 min, and 200 mL min- 1, respectively. The permeances of H2 and N2 at 773 K were 2.9 x 10- 7 and 1.7 x 10-10 mol m- 2 s-1 Pa-1, respectively. The average pore size of the TMMOS-derived silica membrane was estimated to be 0.37 nm by the normalized Knudsen-based permeance method. The hydrothermal stability of the TMMOS-derived membrane after exposure to a gas mixture of steam and H2 at a molar ratio of 3:1 under pressure of 0.3 MPa on the feed side at 773 K indicated that the H2 permeance was higher than that of the dimethoxydimethylsilane-derived silica membrane, and the N2 permeance was almost stable. Furthermore, the pressure on the feed side greatly affected the membrane performance under hydrothermal conditions. The membrane performance became poorer when it was exposed to the same gas mixture under pressure of 1.0 MPa on the feed side at 773 K.
Zwitterionic hydrogels have emerged as eco-friendly anti-fouling materials owing to their superior hydration-mediated resistance to biofouling. Nevertheless, their practical utility remains constrained by intrinsically poor mechanical robustness. Herein, this study proposes a novel strategy to develop novel tough zwitterionic hydrogels by freezing the gels’ polymer network. As a proof of concept, a zwitterionic hydrogel was synthesized via copolymerization of hydrophobic monomer phenyl methacrylate (PMA) and hydrophilic cationic monomer N-(3-dimethylaminopropyl) methacrylamide (DMAPMA), followed by post-oxidation to yield a zwitterionic structure. At service temperature, the rigid and hydrophobic PMA segments remain frozen, while the hydrophilic zwitterionic units maintain substantial water content by osmotic pressure. Synergistically, the zwitterionic hydrogel achieves robust toughness and adhesiveness, with high rigidity (66 MPa), strength (4.78 MPa), and toughness (2.53 MJ/m3). Moreover, the hydrogel exhibits a distinct temperature-dependent behavior by manifesting softer and more stretchable behavior after heating, since the thawing of the gel network at high temperatures increases segmental mobility. Therefore, it achieved satisfactory adhesiveness to substrates (80 kPa). Additionally, the hydrogel demonstrated remarkable anti-fouling performance, effectively suppressing biofilm formation and larval attachment. In summary, this work opens up promising prospects for the development of zwitterionic hydrogels with high application potential.
With the aim of developing thermally/hydrothermally stable silica membranes for H2 separation, dimethoxydimethylsilane-derived silica membranes were prepared via chemical vapor deposition (CVD) at various temperatures. This process employed a substrate having an intermediate layer with a gallium-loaded gamma-alumina coating that had been calcined at 1073 K. The data demonstrate that this intermediate layer was it -self thermally stable at 1073 K and hydrothermally stable at 973 K. A systematic evaluation of membrane performances under thermal/hydrothermal conditions confirmed that membranes prepared at 973 K were more stable than those fabricated at 873 K under dry conditions. In addition, the loss in H2 permeance under hydrothermal conditions was lower in the case that the CVD temperature was 973 K. Hence, to ensure stability, the temperature at which such membranes are employed should be lower than the CVD processing temperature.
Heteroatom doping of carbon materials can effectively alter the microstructure and conductivity, thereby improving the electrochemical performance of lithium-ion batteries (LIBs) hard carbon anodes. Herein, a resin-based hard carbon material (NFHC-1200) with co-doped N and F was prepared by one-step pyrolysis method using phenolic resin as the carbon source and ammonium fluoride as the doped N and F sources. Benefiting from the synergistic effects of co-doping, NFHC-1200 exhibited a wider interlayer distance (0.385 nm), a larger specific surface area (93.31 m2 g−1), and a greater number of Li+ storage active sites (ID/IG = 1.754) when compared to undoped HC-1200 and single-atom doped NHC-1200 hard carbon materials. The results of electrochemical performance demonstrated that the electrochemical properties of NFHC-1200 was significantly improved for co-doped N and F. It exhibited an initial discharge capacity of 614.6 mAh g−1 at 37.2 mA g−1, a reversible capacity of 365.2 mAh g−1 with a capacity retention rate of 97.66
The Hansen solubility parameter (HSP) theory, which includes the Hansen dispersion (D), polar (P), and hydrogen (H) components and a derivative ‘solubility parameter distance, Ra’ parameter, was adopted to evaluate the interaction between different polymers and their various diluents, so as to obtain a valuable and feasible criterion for the diluent selection of the thermally induced phase separation (TIPS) process for the preparation of polymeric membranes. Firstly, a full-scale database of the four HSP parameters of typical polymer-diluent systems was obtained based on a complete literature review about the phase separation process of all the polymer/diluents systems that have been applied to prepare polymeric membranes via TIPS and our additional exploratory experiments for membrane formation mechanism, in which two different phase separation processes including solid to liquid and liquid to liquid were distinguished. Relationships between the Ra parameter and the phase separation behavior were figured out to get a criterion for selecting the single diluent for the typical polymers. Moreover, the diluent selection was extended by adding a second diluent, and a schematic three-dimensional phase diagram was drawn to provide a feasible understanding of the TIPS process of the polymer-binary diluent system. Taking polypropylene (PP) as the representative example, plenty of exploratory experiments for the membrane formation mechanism based on a literature review were conducted to propose a guide based on the Hansen polar and hydrogen solubility component parameters to help select a proper binary diluent system.