Efficient multi-metal cation removal with polysulfone-hydroxyapatite composite spheres in fixed-bed recirculation system

Postharvest strawberry softening is driven by rapid pectin depolymerization, a process accelerated by the fruit's inherently high respiration rate. Although equilibrium modified atmosphere packaging (EMAP) can suppress respiration, conventional systems lack the precision required to dynamically align gas permeability with fruit metabolism. Herein, we engineer a tunable EMAP system by incorporating gas conduction functional units (GCFUs) into a polyether sulfone matrix, enabling quantitatively adjustable CO2/O2 selectivity. The optimized film (P2) spontaneously established an optimal equilibrium atmosphere (5.5% O2, 12.5% CO2) within packages, achieving 80% suppression of respiration for postharvest strawberries. This controlled hypoxic/hypercapnic environment coordinately downregulated key pectin-degrading enzymes, thereby limiting water-soluble pectin accumulation while preserving chelate- and alkali-soluble pectin fractions. Consequently, firmness retention exceeded 70%, and phenotypic deterioration was significantly mitigated. This work bridges material engineering with postharvest physiology, offering a scalable, energy-efficient strategy for extending the shelf life of highly perishable fruits.

Fine-tuned swelling via moderate sulfonation unlocks high-performance and durable sulfonated poly(ether ether ketone) membranes for osmotic energy harvesting

Reconstructing the glomerular filtration barrier in vitro remains a major challenge in kidney research due to the complexity of cellular interactions and membrane properties that regulate glomerular function. In this study, we developed and characterized a human glomerulus-on-a-chip model that recapitulates podocyte-glomerular endothelial cell (ciGEnC) interactions across a membrane resembling the native glomerular basement membrane (GBM). Using polyethersulfone (PES) and polyethylene terephthalate (PET) membranes with distinct physicochemical characteristics, we systematically evaluated how membrane composition modulates cellular attachment, spatial organization, and extracellular matrix (ECM) accumulation and cellular organization at the podocyte-endothelial interface under static and dynamic conditions. PES membranes promoted enhanced adhesion, spreading, and confluence of both podocytes and ciGEnCs. Quantitative fluorescence image analysis revealed significantly higher total cell areas for both cell types on PES compared to PET, with a more balanced endothelial-to-podocyte area ratio (1.77 for PES vs. 3.11 for PET), suggesting improved co-culture equilibrium. The broader pore size distribution, higher equilibrium water content, and elevated nonfreezable water content in PES membranes contributed to stable hydration layers that facilitated cell migration, interaction, and ECM deposition. Confocal imaging demonstrated the formation of continuous, opposing monolayers on PES membranes and ECM accumulation at the interface between the two cell layers. Under physiologically scaled flow rates, both membranes sustained cell attachment and morphology, but PES provided greater resistance to shear-induced detachment, further confirming its suitability for perfusion-based glomerular models. This study highlights the critical role of membrane material properties especially non-freezable hydration capacity and pore morphology in guiding glomerular cell behavior and tissue architecture formation. Our findings establish PES-based GBM microfluidic chips as a promising platform for modeling glomerular filtration, representing an important step toward the development of more physiologically relevant glomerular microfluidic models.

ABSTRACT The inherent hydrophobicity of polysulfone (PSf) membranes frequently leads to membrane fouling issues. To address this limitation, a novel composite membrane was developed by incorporating hydrophilic tannic acid‐modified carbon nanotubes (TCNT). The TCNT nanomaterial was synthesized by functionalizing carbon nanotubes (CNTs)─known for their exceptional organic compound adsorption capacity─with tannic acid (TA), which exhibits mussel‐inspired adhesion properties for surface modification. The TCNT/PSf composite membranes were fabricated via non‐solvent induced phase separation (NIPS). Characterization results demonstrated that increasing TCNT content enhanced membrane porosity, enlarged finger‐like pore structures, and improved surface hydrophilicity (reduced contact angle). The optimal membrane with 7 wt% TCNT loading achieved outstanding performance: 97% bovine serum albumin (BSA) rejection and 450 L m −2 h −1 pure water flux (50% higher than the pristine PSf membrane's 300 L m −2 h −1 ). Moreover, the total fouling ratio ( Rt ) significantly decreased from 84% to 53%, confirming the substantially improved antifouling properties of the TCNT‐modified PSf membranes. The biomimetic functionalization strategy of TA‐CNTs provides a new idea for the development of next‐generation anti‐pollution membrane materials, and its green modification method is in line with the concept of sustainable development.

The sustainable recovery of high-value metals from wastewater has garnered significant attention in light of the circular economy and environmental preservation. Because of its appealing characteristics, membrane separation technology is essential for the sustainable and effective recovery of valuable metals from wastewater, in contrast to conventional methods, which are chemical- or energy-intensive. In this study, a rational design approach was utilized to synthesize a metal-organic framework (MOF) using a deep eutectic solvent (DES) as a mediating medium to control the reaction of framework formation and particle properties. While DESs have been widely used for the physical modification of materials, their role as a chemically modifying medium during MOF synthesis for structural tailoring remains less explored. This synthesized MOF (DM-Zn-PDC@MOF) was further introduced as filler in polysulfone (PSf)-based mixed matrix membranes (MMMs). The performance of DM-Zn-PDC@MOF within the polymer matrix was examined. Several characterization techniques were used to thoroughly analyze the morphological, chemical, and physical characteristics of the MMMs and DM-Zn-PDC@MOF. The addition of the filler material significantly enhanced the membrane characteristics, including pure water flux, hydrophilicity, porosity, surface roughness, pore size, and heavy metal resource recovery in comparison with the pristine membrane. Stable incorporation of the filler within the membrane matrix was indicated by much less filler leaching (<5%) at all concentrations. With DM-Zn-PDC@MOF loading, the pure water flux increasedmore than nine times from 102.8 L/m2h (M-0) to 971.5 L/m2h (M-4). The functionalized membranes showed better flux retention in high-value heavy metal resource recovery using simulated wastewater: 871.8 L/m2h when filtering a Pb(II) ion solution (compared to M-0 with flux 120.6 L/m2h) and 526.8 L/m2h when filtering a Cr(III) ion solution (compared to M-0 with flux 97.1 L/m2h). These values represented approximately 7-fold and 5-fold improvements, respectively. Overall, Pb+2 > Cr+3, but the rejection of Cr(III) ions was also improved, when compared with M-0. The high flux of the membrane makes it easier to process large volumes and concentrate metals in the retentate, turning diluted contaminated streams into a concentrated feedstock for subsequent recovery procedures.

Real-time in situ pH monitoring in the hadal zone is essential for resolving deep-sea carbon dynamics but is severely challenged by extreme hydrostatic pressures and complex biochemical environments. Current sensors often lack the necessary robustness and calibration protocols for full-ocean-depth applications. To address these challenges, we developed a solid-state electrochemical pH sensor system comprising a fouling-resistant sulfonated poly(ether ether ketone)/ionic liquid composite IrOx (SP/IL-IrOx) working electrode and a pressure-tolerant silica-stabilized ionic liquid (Si-StabIL) reference electrode. Using Tris-artificial seawater (Tris-AS) buffers, we established a standardized high-pressure calibration protocol and systematically evaluated sensor performance over the full-ocean-depth pressure range (0.1-120 MPa) under simulated hadal pressure conditions. The sensor exhibited near-Nernstian sensitivity with high reversibility and repeatability, with potential deviations of no more than 1.6 mV, corresponding to less than 0.03 pH units across the investigated pressure range. Long-term reliability was demonstrated by a minimal drift of only 0.01 pH units during continuous operation in the Tris-AS buffer at 120 MPa for 65 h. Crucially, the sensor captured the nonlinear, pressure-driven acidification of simulated hadal-zone seawater during a 7 day pressurization experiment while maintaining stable response in calibration buffers. These results demonstrate the robustness of the sensor system and provide an experimental basis for calibration and pH assessment under simulated full-ocean-depth pressure conditions.

The continuous discharge of oil-laden wastewater poses a critical environmental and industrial challenge, necessitating the development of advanced membrane systems that simultaneously deliver high separation efficiency, strong fouling resistance, effective self-cleaning capability, and low energy consumption. In this study, a multifunctional mixed-matrix membrane based on polyethersulfone (PES), amino-functionalized UiO-66 metal–organic framework (UiO-66-NH2), and graphitic carbon nitride (g-C3N4) was rationally designed and fabricated via a controlled phase-inversion process, enabling a synergistic integration of adsorption and visible-light-driven photocatalytic functionalities. Comprehensive characterisation using FTIR, XRD, and SEM verified the effective incorporation and uniform dispersion of UiO-66-NH2 and g-C3N4 throughout the PES matrix. The resulting composite membrane exhibited markedly improved surface wettability, with a water contact angle of 58 ± 1.2° and an oil contact angle of 94 ± 1.5°, reflecting enhanced hydrophilicity and oleophobicity. Under optimized filtration conditions (0.5 MPa, 25 ± 1°C), the membrane achieved an oil rejection of 99.5 ± 0.3% and a permeate flux of 345.2 ± 10.8 L m⁻2 h⁻1 after 120 min, significantly surpassing pristine PES. Time-, dosage-, concentration-, and pressure-dependent studies revealed stable separation performance and suppressed fouling kinetics. Reusability assessments over ten cycles maintained a flux recovery ratio of 91.1 ± 1.3%, while oil rejection decreased moderately from 99.1 ± 0.4% to 92.8 ± 0.6%. Furthermore, long-term continuous filtration over 12 h exhibited stable operation, with flux retention of approximately 90%, oil rejection above 93.2 ± 0.7%, and a reduced specific energy demand of 0.82–0.91 kWh m⁻3, highlighting the membrane’s promise for sustainable oily wastewater remediation.Supplementary InformationThe online version contains supplementary material available at 10.1038/s41598-026-55643-1.

Synergistic optimization of pore structure and hydrophilicity for an ultrathin, high-safety composite diaphragm toward high-current, durable alkaline water electrolysis.

Fouling limits the performance and lifetime of polyethersulfone (PES) ultrafiltration membranes. We investigated the effect of blending polyaniline (PAni·DBSA) into PES on membrane morphology, wettability, permeability and antifouling behavior, and we evaluated a simple electrochemical cleaning protocol for fouled membranes. A series of PES/PAni·DBSA membranes with different PAni loadings were characterized by SEM, BET, AFM, contact angle, TGA and porosity analysis. Initial water flux (J), bovine serum albumin (BSA) rejection (RR) and flux recovery ratio (FRR) were measured in a dead-end filtration cell. Electrochemical cleaning was applied to selected fouled membranes, and post-cleaning flux and rejection were measured. PAni·DBSA incorporation produced a hierarchical pore structure and altered near-surface texture. Contact angle decreased from 76° to 54°, and swelling increased for intermediate PAni loadings. Initial pure-water fluxes ranged from 5.9 to 39.3 L·m-2·h-1. When expressed as absolute percentages, the best performing membrane in terms of reversible fouling recovered 8.12 times of its initial flux. Multivariate analysis indicates that surface hydration and height distribution explain more variance in FRR than Rq alone, consistent with a synergistic role of texture and wettability. Electrochemical treatment substantially increased both flux and rejection for tested membranes, indicating effective foulant mobilization.

Intelligent proton-conducting metal-organic framework (MOF) membranes, with dynamically and remotely controllable proton conduction, exhibit considerable potential for advanced applications such as sensors. In this study, a unique TCPP∈Im-UiO-66 synthesized by porphyrin (TCPP) and imidazole (im) ligands was used to prepare photoacid-doped TCPP∈Im-UiO-66@PCN (PCN = photoacid) material by the photoacid impregnation method. To improve proton conductivity and practicality, the TCPP∈Im-UiO-66@PCN hybrid membrane was fabricated by blending with sulfonated poly(ether sulfone) (SPES). Under light exposure, the PCN structure transforms from the open-loop spiropyran (MC) form to the closed-loop spiropyran (SP) form. When exposed to 375 nm ultraviolet light at room temperature, the proton transport channels formed by PCN in the composite membrane will be cut off. The TCPP∈Im-UiO-66@PCN film of the 5% composite film shows obvious light response behavior, which is 0.12 S·cm-1 in the absence of light and 0.017 S·cm-1 in the illumination. The optimal 5 wt % composite membrane achieves a maximum proton conductivity ON/OFF switching ratio of 7.1, which represents the largest photoswitching ratio among all prepared membranes. Therefore, our research has developed a stable proton-conducting membrane integrated with photoacids, which not only offers a new strategy for proton exchange membranes in fuel cells but also provides a novel approach for applications in remote photoproton sensing.

To meet the demands of high-power-density electronics, high-temperature-resistant polymer dielectrics are essential for ensuring reliable operation. Although doping with molecular semiconductors effectively improves the high-temperature performance of polymer dielectrics, the semiconductors often exist in an isolated, discontinuous distribution. Beyond the inherent issues of poor dispersion and interfacial incompatibility, this morphology may also form conductive pathways under excessive doping, resulting in severe degradation of dielectric properties. Herein, we incorporated chiral molecules e.g., (13bR)-5,6-dihydro-5-(trans-4-propylcyclohexyl)-4H-dinaphtho[2,1-f:1',2'-h][1,5]dioxonin (R5011) and its chiral enantiomer (S5011) into polyethersulfone (PES) to construct supramolecular chiral co-assembly structure. Through π-π stacking interactions, the chiral molecules give rise to an amplified and emergent chiral expression at the macroscopic polymer chain level. The local twisted structure formed by chiral amplification leads to an enlarged torsional angle between the sulfone-flanking phenyl rings and constructs carrier traps, thereby significantly enhancing the breakdown strength. Ultimately, the co-assembly PES achieved high energy densities of 8.73Jcm-3 (150°C) with efficiency of 90% and maximum discharge energy density of 10.08Jcm-3 at 150°C. Furthermore, stacked film capacitors based on the PES composite films demonstrated excellent high-temperature capacitance stability at 150°C. This work demonstrates a novel approach to designing advanced polymer dielectrics through supramolecular interactions.

Membranes applied in alkaline flow batteries suffer swelling from spontaneous polymer chain motion, which degrades ion selectivity and mechanical strength. Here, we employ a large language model (LLM)-driven screening workflow to efficiently shortlist crosslinkers from a curated knowledge base, guiding the rational design of a hybrid dual network (H-DN) membrane. The workflow identifies N,N,N',N'-tetramethylethylenediamine as the optimal candidate to build a robust, chemically crosslinked polysulfone network interpenetrated within a widely used sulfonated poly(ether ether ketone) (SPEEK) matrix. Mechanistically, the in situ formed quaternary ammonium motifs strongly ion-pair with sulfonic acid groups, effectively suppressing chain motion without blocking ion transport channels. Consequently, the H-DN membrane exhibits a 68% reduction in swelling and an ultra-high wet-state hardness of 216MPa (a sixfold increase over SPEEK), while retaining high ionic conductivity (10.7 mS cm-1). Enabled by this mechanically robust and highly selective architecture, the alkaline zinc-iron flow battery achieves an energy efficiency of 88.87% at a challenging areal capacity of 240 mAh cm-2 and operates stably for over 820h without dendrite-induced failure, which surpassed the commercial Nafion212 and SPEEK benchmarks by threefold and sevenfold, respectively. This work establishes a paradigm for LLM-accelerated material discovery in addressing the stability-selectivity dilemma of ion-exchange membranes.

Forward osmosis (FO) membranes have garnered widespread research interest in water treatment, yet their permeability-selectivity trade-off, internal concentration polarization, and membrane fouling remain critical challenges. Herein, a chitooligosaccharide/polydopamine (COS/PDA) co-deposition strategy was proposed to modify polyethersulfone (PES) substrates for constructing high-performance thin-film composite (TFC) FO membranes. COS suppressed excessive PDA aggregation, reduced substrate roughness, and improved substrate hydrophilicity. This substrate modification regulated interfacial polymerization by increasing the adsorption capacity for m-phenylenediamine (MPD) while slowing its diffusion rate, thereby forming thinner, smoother, and more densely crosslinked polyamide (PA) layers. The optimized C4P1-TFC membrane delivered water fluxes of 42.2 and 23.5 L m-2 h-1 in pressure-retarded osmosis (PRO) and FO modes, respectively, representing 43.1% and 40.2% improvements over the pristine membrane. Its specific salt flux decreased to 0.07 and 0.15 g L-1 in the two modes, respectively, suggesting enhanced selectivity. Meanwhile, the C4P1-TFC membrane showed antibacterial rates of 85.7% against Escherichia coli and 86.9% against Staphylococcus aureus, together with improved antifouling performance against bovine serum albumin and lysozyme. This work presents a simple and effective co-deposition approach for simultaneously improving the separation, antibacterial, and antifouling performance of TFC FO membranes, showing promising potential for practical applications.

High-performance polyethersulfone (PES) ultrafiltration membranes integrating antibacterial activity and antifouling performance were fabricated via the in situ construction of bimetallic polyphenol networks (BMPNs) throughout the membrane architecture. Tannic acid (TA) functioned as a multifunctional molecular bridge, functionalizing silver metal–organic frameworks (Ag-MOFs) to yield hydrophilic T-Ag-MOFs and chelating Fe3+ ions from the coagulation bath to form a polyphenol network during phase inversion. T-Ag-MOF incorporation generated asymmetric morphologies featuring highly porous surfaces and sponge-like cross-sections, improving pure water permeability, mechanical integrity, and bovine serum albumin (BSA) rejection. TA-mediated functionalization increased hydrophilicity, imparted a negative surface charge, suppressed nonspecific protein adhesion, and enhanced flux recovery with low irreversible fouling. At an optimal loading of 0.4 wt%, the resultant T-Ag-MOF/Fe3+/PES composite membrane achieved a pure water permeability of 593.4 L m−2 h−1 bar−1—1.77-fold higher than that of the pristine PES control—while sustaining a BSA rejection of 96.5%. Notably, interfacial compatibility between the T-Ag-MOFs and PES matrix was enhanced, facilitating strong, covalent-like filler–matrix adhesion. Moreover, the composite membrane delivered synergistic multifunctionality, including exceptional long-term aqueous stability, precisely tuned Ag+ release kinetics, and potent antibacterial activity, as evidenced by negligible uncontrolled ion leaching and a lack of structural degradation under prolonged hydration.

Polymeric membranes are widely investigated for CO2 separation; however, their performance is often limited by the permeability–selectivity trade-off. Incorporating metal–organic frameworks (MOFs) and designing composite membrane architectures are promising strategies to overcome these limitations. This study aims to evaluate the effect of incorporating MOF-74 (Cu and Ni variants) into a polydimethylsiloxane (PDMS) selective layer supported on a polysulfone (PSF) membrane for enhanced CO2/N2 separation performance. Dual-layer PDMS/PSF composite membranes were fabricated via phase inversion for the PSF support, followed by solution casting of the PDMS/MOF layer. The developed membrane architecture introduces a synergistic design that combines the mechanical robustness of PSF with the selective transport capability of PDMS and the strong CO2 affinity of MOF-74, offering an effective strategy for improving gas separation efficiency. Gas permeation performance was assessed using single-gas CO2 and N2 measurements at feed pressures of 2–5 bar. The incorporation of MOF-74 improved CO2 transport properties, with the 1 wt.% Cu-MOF-74 composite membrane achieving a CO2 permeance of 912.5 GPU and a CO2/N2 ideal selectivity of 94.75. The dual-layer configuration significantly enhanced permeance compared with unsupported mixed-matrix membranes while maintaining selectivity. Additionally, the composite membranes exhibited improved mechanical strength due to the PSF support layer. The findings demonstrate that dual-layer PDMS/PSF composite membranes incorporating MOF-74 provide a promising proof-of-concept approach for improving CO2 separation performance. Further studies involving mixed-gas testing and long-term stability are required to assess their practical applicability.

The long-term performance of electrostatic fibrous filters is inherently limited by charge dissipation. Conventional regeneration strategies often rely on mechanical contact, which risks material damage due to localized stress. Here, we present a non-contact acoustic approach that effectively rejuvenates both electrostatic charge and filtration performance in nanofiber filters. Using electrospun poly(vinylidene fluoride) (PVDF)-polysulfone (PSF) membranes, we first removed the embedded charges, which reduced the PM0.3 filtration efficiency to ∼75% (solid) and ∼74% (oil), with a pressure drop of 96 Pa. Subsequent acoustic stimulation (100 Hz, 110 dB, 10 min) restored the efficiency to 99.99% for solid and 92.90% for oily particles, while lowering the pressure drop to 45 Pa, performance that matches that of the pristine, as-spun membranes. This recovery stems from sound-induced fiber vibration, which activates a synergistic piezoelectric-triboelectric mechanism within the microphase-separated composite, replenishing surface charge and expanding the pore structure. The process is repeatable over 30 cycles without decay and also enhances back-pulse cleaning. By introducing acoustic energy as a distinct, non-contact regeneration regime, this work provides a scalable pathway toward energy-efficient, durable, and high-performance air filtration systems.

ABSTRACT Polymer–solvent compatibility is commonly evaluated using Hansen solubility parameters (HSPs), where the relative energy difference (RED) is typically interpreted as a deterministic threshold separating good and poor solvents. Experimental evidence shows that polymer solubility evolves gradually in Hansen space, particularly near the solubility boundary, where swelling and partial dissolution are common. In this work, a probabilistic reformulation of the RED criterion is proposed that preserves the geometric structure of Hansen space while interpreting RED as a continuous descriptor mapped to a probability of solubility. Solubility parameters and radii are estimated through numerical optimization using objective functions that balance geometric consistency and probabilistic reliability. Experimental uncertainty associated with partially soluble systems is incorporated through a weighted encoding scheme. The method is evaluated using literature datasets for thermoplastic polyurethanes, poly(ether sulfone), lignin, and waterborne polyurethane, and further examined using experimental data for microcrystalline cellulose, where swelling dominates over true dissolution. In the waterborne polyurethane system, the optimized solubility radius decreases from 16.3 to 7.8 MPa 1/2 , yielding a more selective solubility domain. Machine learning models trained in the Hansen space provide decision boundaries that, when approximated by isoprobability contours ( p ≈ 0.5), agree with the optimized solubility sphere.

The comparison of the ability of poly(phenylene sulfone) (PPSU), a recently introduced alternative membrane polymer, with established poly(ether sulfone) (PESU), both in combination with tailored amphiphilic block copolymer additives to improve ultrafiltration (UF) membrane separation and anti-fouling performance is the focus of this work. Different poly(alkylene oxide)-containing tri- and multiblock polymers with hydrophobic blocks analogous to the respective base polymer, PPSU or PESU, of varied length were used as additives in the casting solution. Membranes were subsequently prepared via film casting and a liquid non-solvent-induced phase separation (NIPS) process. The rheological properties and thermodynamic stability of the casting solutions were investigated. At the same mass concentration, PPSU-based casting solutions show overall higher viscosity that is also more sensitive to the presence of additives compared with PESU-based solutions. PPSU-based casting solutions also have lower tolerance to non-solvents. By adding certain block copolymers in ratios of up 10 wt.% relative to the base polymer, it is possible to increase the UF performance of the membranes of PPSU and PESU. An increase in the block length of the hydrophobic block of PESU leads to a reduction in pure water permeance (PWP), whereas for PPSU, PWP is increased by the addition of additives. Especially additives with shorter PESU or PPSU block length, i.e., with a larger fraction of poly(ethylene oxide) blocks in the casting solution, seem to act as additional pore-forming agents. The water contact angle can be decreased for both additive systems, indicating a more hydrophilic membrane surface. Finally, using flower soil extract as a model substance for surface water, interesting candidates of additives that enable fouling reduction with competitive UF performance were identified for PESU and PPSU membranes.

ABSTRACT The purpose of this study is to prepare a waterborne epoxy resin emulsified asphalt with better high temperature rheological properties as a tack coat material for thin-layer overlay technology. Therefore, styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS) and polysulfone (PSF) with the content of 2%, 4% and 6% were selected to modify and toughen waterborne epoxy resin emulsified asphalt (EA-WER) with the content of 7.5% of waterborne epoxy resin (WER). The dynamic shear rheological test (including temperature scanning test and frequency scanning test) and fluorescence microscope test were carried out to systematically evaluate its rheological properties. The results show that the addition of three toughening agents improves the high temperature deformation resistance of EA-WER, among which SBS waterborne epoxy resin emulsified asphalt (EA-SBS-WER) is the best, SBR waterborne epoxy resin emulsified asphalt (EA-SBR-WER) is the second, and PSF waterborne epoxy resin emulsified asphalt (EA-PSF-WER) has the smallest relative improvement. The optimum content of SBS is 6%, and the optimum content of SBR and PSF is 4%. The fitted main curve further confirms the optimal dosage.