Hybrid Membranes Research Articles

Supramolecular Modifying Nafion with Fluoroalkyl-Functionalized Polyoxometalate Nanoclusters for High-Selective Proton Conduction.

Fluoroalkyl-grafted polyoxometalate nanoclusters are used as supramolecular additives to precisely modify the ionic domains of Nafion, which can increase the proton conductivity and selectivity simultaneously. The resulting hybrid membranes show significantly enhanced power density in fuel cells and improved energy efficiency in vanadium flow batteries.

MOFs/MXene nano-hierarchical porous structures for efficient ion dynamics

Nature's various hierarchical structures exhibit exceptional performance in enhancing mass transport. However, how to bionic nano-hierarchical structures to enhance ion dynamics and achieve charge regulation is a significant challenge. Herein, a nano-hierarchical porous hybrid membrane inspired by nature was designed by integrating 1D metal-organic frameworks (MOFs) on the 2D MXene substrate utilizing MOF nanoparticles with tailorable positive and negative surface charges. The synergistic effects of the bioinspired nanohierarchical porous structure and surface charge interactions significantly enhance the performance and stability of the nanoconfined membrane, as corroborated by experimental characterizations and theoretical simulations. As a result, the optimized nanohierarchical porous membrane exhibits high a cation selectivity of 0.95, an outstanding power density of 35.04 W m−2, and excellent stability over one month. Synergizing enhanced mass transport and ion dynamics in nano-hierarchically structured materials with tailored charge improves osmotic power generation efficiency and benefits logic circuits with controlled charge transport.

Preparation of sulfonated poly(arylene ether ketone sulfone) PEMs with enhanced proton conductivity by introducing ionic liquid impregnated MOFs

In this research, sulfonated poly(arylene ether ketone sulfone) containing -COOH groups (C-SPAEKS) was chosen as the substrate, and ionic liquid functionalized MOFs (UiO-66-AS@ILs) were selected as fillers to prepare C-S-U-AS@ILs hybrid membranes (The term “C-S-U-AS@ILs” signifies C-SPAEKS with an incorporated ionic liquid functionalized UiO-66-AS@ILs). The UiO-66-AS@ILs and C-S-U-AS@ILs hybrid membranes were characterized by 1H NMR, FT-IR, PXRD and SEM. The prepared membranes exhibited suitable water uptake and swelling ratios, and the C-S-U-AS@ILs-5 % hybrid membrane possessed superior proton conductivity (0.197 S cm−1 at 90 °C) was much higher than C-SPAEKS (0.156 S cm−1 at 90 °C) and Nafion 117 (0.110 S cm−1 at 90 °C). Moreover, the C-S-U-AS@ILs-5 % hybrid membranes’ power density up to 474.24 mW cm−2, significantly higher than that of C-SPAEKS (220.88 mW cm−2) under the same conditions. These results reflect that the hybrid membranes exhibited superior properties and fit the standards of proton exchange membranes.

Toward highly ionic polyelectrolyte membrane: Synthesis, characterization, membrane performance and theoretical studies of PVDF-g-PAN/PAMPS hybrid membranes

Novel highly ionic polyvinylidene fluoride (PVDF) membranes grafted with an acrylonitrile monomer to yield the target (PVDF-g-PAN) via radical polymerization and then blended with the amphiphilic copolymer poly (2-acrylamido-2-methyl-1-Propane sulfonic acid (PAMPS) via physical interactions (PVDF-g-PAN)/(PAMPS), were designed and constructed. The new functional groups obtained (fluoride, nitrile, and sulfonic functions) were confirmed via FTIR analysis, and the prepared membranes were characterized using SEM, TGA, tensile strength, water contact angle, and mechanical stability instruments. The essential characteristics of the polyelectrolyte membranes, including the IEC, ionic conductivity, methanol permeability, thermal stability, and high mechanical qualities, were examined. It was discovered that, the oxidative stability of the modified membrane (P3) with a high concentration of conductive PAMPS affected the percentage of weight loss (5.25 %) at the end of 24 h. In addition, the water absorption capacity increased with increasing in the concentration of PAMPS. Similarly, the highly concentrated PAMPS modified membranes (P3) have an ionic exchange capacity and proton conductivity equal to IEC= 1.93 meq/g, which is greater than that of the Nafion membrane by 0.91 meq/g. Furthermore, appropriate DFT theoretical studies such as EHOMO, ELUMO, energy band gap and dipole moment (µ) were thoroughly examined and employed to validate the highly ionic system. It was found that, the energy band gap of PVDF-g-PAN/PAMPS was 5.19 eV, which is lower than that of the grafted polymer value (7.17 eV), confirming that the electrons are transferred readily from the HOMO level to the LUMO level. In addition, the dipole moment of the PVDF-g-PAN/PAMPS was 7.10 Debye, which is greater than the dipole moment value of the grafted polymer (2.07 Debye), indicating the highly ionic character of the hybrid polymer. Finally, the promising results obtained demonstrated favorable film-forming and structural properties, making it a promising option for polyelectrolyte membranes. It also has the added advantage of being cost-effective and can be applied in many electrochemical applications.

Development of a hydrogen permselective silica membrane and its application to the thermochemical water splitting method

Abstract The thermochemical water splitting IS process is one of the hydrogen production method to use a heat directly. The temperature of the thermal decomposition of water (4000 K) can be reduced under 700 K by introducing I2 and SO2 as recycling catalysts. One of the problems in the IS process is that the conversion of the HI decomposition reaction is low at about 20%. If a membrane reactor with the H2 permselective membrane is applied to the HI decomposition reaction, the hydrogen can be extracted to improve the HI conversion. We focus on a counter diffusion CVD method for the preparation method of the membranes. Two reactants (e.g. silica precursor and oxidant) are provided at the opposite side of the porous substrates and hybrid silica is deposited inside the pore of the substrate. The pore sizes are controlled by introducing organic functional groups to silica precursor. In this study, the silica hybrid membrane with high H2 permeation performance and high H2/HI selectivity were developed by introducing organic functional groups. Effects of the organic functional groups were summarized by using a pore model. The HI gas and other inorganic gases permeation performance were tested through silica hybrid membranes.

Hydrogel-based hybrid membrane enhances in vitro ophthalmic drug evaluation in the OphthalMimic device

Envisaging to improve the evaluation of ophthalmic drug products while minimizing the need for animal testing, our group developed the OphthalMimic device, a 3D-printed device that incorporates an artificial lacrimal flow, a cul-de-sac area, a moving eyelid, and a surface that interacts effectively with ophthalmic formulations, thereby providing a close representation of human ocular conditions. An important application of such a device would be its use as a platform for dissolution/release tests that closely mimic in vivo conditions. However, the surface that artificially simulates the cornea should have a higher resistance (10 min) than the previously described polymeric films (5 min). For this key assay upgrade, we describe the process of obtaining and thoroughly characterizing a hydrogel-based hybrid membrane to be used as a platform base to simulate the cornea artificially. Also, the OphthalMimic device suffered design improvements to fit the new membrane and incorporate the moving eyelid. The results confirmed the successful synthesis of the hydrogel components. The membrane’s water content (86.25 ± 0.35 %) closely mirrored the human cornea (72 to 85 %). Furthermore, morphological analysis supported the membrane’s comparability to the natural cornea. Finally, the performance of different formulations was analysed, demonstrating that the device could differentiate their drainage profile through the viscosity of PLX 14 (79 ± 5 %), PLX 16 (72 ± 4 %), and PLX 20 (57 ± 14 %), and mucoadhesion of PLXCS0.5 (69 ± 1 %), PLX16CS1.0 (65 ± 3 %), PLX16CS1.25 (67 ± 3 %), and the solution (97 ± 8 %). In conclusion, using the hydrogel-based hybrid membrane in the OphthalMimic device represents a significant advancement in the field of ophthalmic drug evaluation, providing a valuable platform for dissolution/release tests. Such a platform aligns with the ethical mandate to reduce animal testing and promises to accelerate the development of safer and more effective ophthalmic drugs.

Dehydration of bioethanol using novel polysulfone (PSF)/nonionic surfactants hybrid membranes

This study focuses on developing a novel polysulfone (PSF) dense hybrid membrane modified with nonionic surfactants, Tween 20 (T20) and Triton X-100 (X100), for improved pervaporation (PV) dehydration of bioethanol. The modified membranes were then examined for their ethanol dehydration performance, microscopy and spectroscopy characteristics, surface charge, mechanical and roughness properties, crystallinity structure, differential scanning calorimetry (DSC), swelling, and contact angle (CA) analysis. The free volume structure of the membranes was assessed using positron annihilation lifetime spectroscopy (PALS) and Doppler broadening spectroscopy (DBS). A significant discovery from this analysis was the semi antiplasticizing effect observed when surfactants were added to the PV membranes. The PV results revealed that incorporating 0.5 wt% T20 into PSF significantly improved the total flux and PSI of PSF/T20 to 226.35 g/m2 h and 46578 g/m2 h, respectively. Similarly, the total flux and PSI of hybrid membranes containing X100 increased to 110.19 g/m2 h and 43680 g/m2 h. Consequently, the developed PSF/T20 membranes demonstrated more significant potential for bioethanol dehydration compared to PSF/X100 membranes.

Oxygen vacancy mediated photocatalysis of Ti3C2 MXene quantum dots/W18O49 hybrid membrane for peroxymonosulfate-enhanced oxidation degradation

Photocatalytic membrane technology shows great prospects in water decontamination. Coupling photocatalysis with peroxymonosulfate (PMS) can boost oxidation capacity by combining their superiorities sufficiently. Herein, 0D Ti3C2 MXene quantum dots (TMQDs) embedded oxygen vacancy-rich 3D sea urchin-like W18O49 microspheres (OTW) were synthesized via facile interface engineering combined with green plasma etching strategy. The visible-light driving flow-through membrane reactor was capable of degrading cyclophosphamide, a typical anticancer drug, and other common pollutants (5-fluorouracil, carbamazepine, bisphenol A, rhodamine B), with the removal and mineralization efficiencies of 10 μM pollutants reaching over 99 % and 63 %−79 % in 60 min with 0.5 mM PMS. Moreover, the long-term reliability of OTW membrane was validated through continuous treatment of 20 L sewage. Significantly, the newly designed photocatalytic membrane exhibited good tolerance to wide pH ranges, common coexisting substances in water, and various actual water matrix. The results of experimental and DFT theoretical calculations revealed that Schottky junction formed on the TMQDs/W18O49 interfaces and tunable O-defects could optimize electronic configuration, improve solar energy utilization, prevent photogenerated carriers’ recombination, promote H2O and PMS dissociation, making it possible that more •OH and SO4•− radicals participated in the oxidation degradation reaction. This study offers a design idea for preparing efficient and robust photocatalytic membrane via interface engineering and defect engineering strategies, which might contribute to bridging the translational gap between emerging photocatalytic techniques and practical environmental applications in near future.

Targeted therapy of glomerulonephritis via salvianolic acid b-loaded biomimetic hybrid nanovesicles driven by homing

BackgroundMesangial cell (MC)-mediated immune inflammatory injury is a basic pathological process in glomerulonephritis. However, due to the limited drug accumulation and serious adverse effects, it remains challenging to explore a rational delivery system integrating high efficiency and low toxicity to deliver anti-inflammatory drugs to the glomerular MC region. ResultsSalvianolic acid B (SAB)-loaded hybrid membrane biomimetic nanovesicles (SAB@HMVs) were developed by fusing erythrocyte membrane nanovesicles with mesenchymal stem cells biomimetic membrane nanovesicles. SAB@HMVs had a spheroidal structure, low cytotoxicity, particle size of 143.83 ± 1.33 nm and exhibited a high drug loading capacity (7.02 %±0.30 %) along with a good sustained release function. The in vitro anti-inflammatory results revealed that HMVs were effectively taken up by MCs and showed significant anti-inflammatory activity. Furthermore, in vivo pharmacodynamic studies revealed that SAB@HMVs could deliver SAB to kidney tissue and elicit an effective anti-inflammatory response to improve the pathological changes in the glomerular mesangial region, significantly reducing the levels of cytokines and alleviating kidney inflammation. Especially, noteworthy was the observation that SAB@HMVs augmented the renal delivery of SAB, downregulated the gene expression of p38 MAPK and NF-κB, inhibited the levels of MMP9 and TNF-α proteins as well as elevated the level of iκB protein, indicating that the anti-inflammatory mechanism of SAB@HMVs should be based on regulating MAPK and NF-κB signaling pathways. ConclusionWe provided a novel strategy to increase nanovesicles accumulation in MCs with the potential to exert anti-inflammatory regulatory effects in glomerulonephritis. Furthermore, this biomimetic hybrid membrane loaded with pure drugs may offer a functional platform to address multiple clinical needs.

Cellulose triacetate-based mixed matrix membranes for concurrent removal of arsenate and arsenite from groundwater

Arsenic is one of the most dangerous groundwater contaminants whose effective removal is a major challenge for environmental scientists. Herein, several cellulose triacetate-based hybrid membranes are synthesized by adding different dosages (10, 30, and 50 wt%) of chitosan or chitosan-stabilized iron nanosheets. The fabricated membranes are characterized by advanced analytical tools such as AFM, SEM, FTIR, BET, TGA, zeta potential, and XRD. The enhancement in hydrophilicity and improved antifouling are evaluated by porosity, water uptake, contact angle, permeability tests, and bovine serum albumin (BSA) studies. At neutral pH, the cellulose triacetate-chitosan 50 % (CTA-CH 50 %) removed 85.13 % As(III) and 87.20 % As(V) at 67.23 L.m−2.h−1 permeability. On the other hand, cellulose triacetate-chitosan iron nanosheets 50 % (CTA-CIN 50 %) removed 91.30 % As(III) and 84.24 % As(V) at 62.35 L.m−2.h−1 permeability. The synthesized membranes efficiently removed arsenic from real groundwater taken from different Pakistani cities. The membranes are synthesized through a low-cost and scalable method, making it convenient for industrial-level applications.

Development and evaluation of a hybrid membrane condenser for water recovery from cooling tower plume

Cooling towers discharge a tremendous amount of water vapor from industries into the atmosphere. Recovering this water will increase efficiency, contribute to water security and industrial sustainability. Thus, suitable technology is needed. This study investigates the feasibility of a microporous hydrophobic propylene membrane to recover water from an artificial humid gas, representing water vapor from a cooling tower. Water was used as a cooling medium in the permeate side of the membrane module. Experimental results showed that water vapor condensed on the surface of the membrane on the feed and the permeate sides. Thus, the membrane module worked as a conventional membrane condenser (MCo) and a transport membrane condenser (TMC) simultaneously, resulting in high water recovery, reaching up to four times that of the TMC mode alone. Key factors influencing rate of condensation and water recovery, such as feed velocity and cooling water temperature, are thoroughly investigated. As feed velocity increased, the rate of condensation also increased, but the water recovery decreased. Lowering the cooling water temperature increased the rate of condensation as well as the water recovery. The results show a maximum water recovery of 75 % under optimal conditions, highlighting the novel and improved performance of the proposed configuration for water vapor recovery from cooling tower plumes compared to previous MCo studies.

Investigations of nanomaterial-based membranes for efficient removal of contaminants from wastewater via membrane distillation: a critical review

The requirement for wastewater treatment is paramount in ensuring environmental sustainability and safeguarding public health. As industrialization and urbanization accelerate, the volume of wastewater generated continues to increase, containing a diverse range of pollutants and contaminants. Untreated wastewater poses serious threats to ecosystems, water bodies, and human communities, leading to pollution, waterborne diseases, and ecological imbalances. Effective wastewater treatment becomes essential to mitigate these adverse effects by removing or reducing pollutants before discharge into natural water sources. This process helps to preserve water quality, protect aquatic life, and maintain the overall health of ecosystems. Membrane distillation (MD) has emerged as a promising technology for wastewater treatment, offering an innovative approach to address the challenges associated with conventional treatment methods. In MD, a hydrophobic membrane serves as a selective barrier, allowing water vapor to pass through while preventing the passage of contaminants. This paper offers an extensive overview of the latest advancements in nanotechnology and membrane distillation applied in wastewater treatment. We will delve into different types of nanomaterials that have been used to enhance the properties of MD membranes, such as nanocomposites, nanoparticles, and nanofiber membranes. We also explore the mechanisms by which these nanomaterials improve the separation efficiency, anti-fouling properties, and durability of MD membranes. Additionally, we highlight the potential of hybrid membranes that combine different types of nanomaterials for further improving the performance of MD in wastewater treatment. We provide examples of recent studies that have investigated the use of hybrid membranes, including carbon nanotube-graphene oxide hybrid membranes, nanocomposite nanofiber membranes, and silver nanoparticle-embedded membranes. We also identify some areas for future research and development, such as the scale-up and commercialization of nanotechnology-based MD systems. In summary, this review paper highlights the potential of nanotechnology to enhance the performance of MD in wastewater treatment, leading to improved water quality and a cleaner environment.

A Fully Biodegradable and Ultra‐Sensitive Crack‐Based Strain Sensor for Biomechanical Signal Monitoring

AbstractA fully biodegradable, ultra‐sensitive, and soft strain sensor is pivotal for temporary, real‐time monitoring of microdeformations, crucial in disease diagnosis, surgical precision, and prognosis of muscular, and vascular conditions. Nevertheless, the strain sensitivity of previous biodegradable sensors, denoted by gauge factor (GF) up to ≈100, falls short of requirements for complex biomedical monitoring scenarios, specifically monitoring cardio‐cerebrovascular diseases with microscale variations in vascular surface strain. Here, a fully biodegradable, ultra‐sensitive crack‐based flexible strain sensor is introduced achieving GF of 1355 at 1.5% strain through integration of molybdenum (Mo) film, molybdenum trioxide (MoO3) adhesion layer, and polycaprolactone (PCL) substrate. Analysis of crack morphology of biodegradable thin‐film metals, including Mo, tungsten (W), and magnesium (Mg), reveals material‐dependent sensitivity and repeatability of crack‐based strain sensors. The effect of the adhesion layer and polymer substrate is also investigated. Overall morphological studies on the sensor present a comprehensive understanding of metal film cracking behavior and corresponding performance characterization, showing significant potential for highly sensitive sensors. A hybrid membrane composed of candelilla wax (Cw), beeswax (Bw), and polybutylene adipate‐co‐terephthalate (PBAT) is introduced to provide hydrophobic, yet flexible encapsulation. In vivo, short‐term (≈3 days) monitoring of vascular pulsatility underscores the potential of the sensing tool for rapid, accurate, and temporal disease diagnosis and treatment.

Fabrication of cobalt-iron Prussian blue analogues functionalized hybrid membranes for efficiently capturing Tl from water: Performance and mechanism

As trace levels of thallium (Tl) in water are lethal to humans and ecosystems, it is essential to exploit advanced technologies for efficient Tl removal. In response to this concern, an innovative composite membrane was developed, incorporating polytetrafluoroethylene (PTFE) and featuring a dual-support system with polydopamine (PDA) and polyethyleneimine (PEI), along with bimetallic Prussian blue analogues (Co@Fe–PBAs) as co-supports. The composite membrane exhibited an exceptional Tl+-adsorption capacity (qm) of 186.1 mg g−1 when utilized for the treatment of water containing low concentration of Tl+ (0.5 mg⋅L−1). Transmission electron microscopy displayed the obvious Tl+ mapping inside the special hollow Co@Fe–PBAs crystals, demonstrating the deep intercalation of Tl+ via ion exchange and diffusion. The Tl+-adsorption capability of the composite membrane was not greatly affected by coexisting Na+, Ca2+ and Mg2+ as well as the tricky K+, indicating the excellent anti-interference. Co-doped PBAs enhanced ion exchange and intercalation of the composite membrane with Tl+ leading to excellent Tl+ removal efficiency. The composite membrane could efficiently remove Tl+ from thallium-contaminated river water to meet the USEPA standard. This study provides a cost-effective membrane-based solution for efficient Tl+ removal from Tl+-containing wastewater.

Construction of X-Co-tri@SSNF reinforced PPS composite proton exchange membranes and their performance in fuel cells

In this study, we pioneered the introduction of benzophenone (DPK) as a solid solvent into polyphenylene sulfide (PPS) melt-blown, which effectively reduced the PPS melt-blown processing temperature and significantly improved the coefficients of variation of PPS melt-blown nonwoven materials. X-Co-tri@SSNF proton exchange membranes with excellent performance were prepared by functionalized modification of PPS melt-blown fabric as a substrate. The structure and properties of X-Co-tri@SSNF proton exchange membranes were systematically characterized. The results demonstrate that the 1-Co-tri@SSNF PEM exhibited a high proton conductivity of 0.183 S cm−1 at 80 °C and high humidity, significantly higher than the commercial Nafion 117 (0.135 S cm−1). Due to the heat resistance of PPS itself and the continuous dense network structure substrate of PPS nonwoven fabrics as well as the high compatibility with the membrane casting liquid, the hybrid membrane interfaces were tightly connected, so it makes the hybrid membrane perform better in terms of mechanical stability (tensile strength of 36.7 MPa), methanol permeability (4.78 × 10−7 cm2 s−1), selectivity (16.32 × 104 S s cm−3), and thermal stability (thermal decomposition temperature of around 450 °C). In addition, the 1-Co-tri@SSNF membrane electrode module exhibited excellent single-cell performance with an open-circuit voltage of 629.91 V and a peak power density of 96.29 mW cm−2 (162.9 % higher than that of Nafion 117). Therefore, the composite PEM with PPS melt-blown fabric as the matrix has a more environmentally friendly process than the commercial Nafion 117 membrane, a theoretical guidance for advancing the large-scale production of low-cost PEM.

Economic evaluation of submerged anaerobic hybrid membrane bioreactor operating at mesophilic temperature.

A laboratory-scale mesophilic submerged anaerobic hybrid membrane bioreactor (An-HMBR) was operated for 270days for the treatment of high-strength synthetic wastewater at different hydraulic retention times (HRTs) (3days, 2days, 1day, and 0.5days). Chemical oxygen demand (COD) removal efficiency of 92% was obtained with methane yield rate of 0.18 LCH4/g CODremoval at 1-day HRT. The results of lab scale reactor at 1-day HRT were utilized for upscaling and cost analysis. Cost analysis revealed that the total capital cost comprised tank system (48%), membrane cost (32%), screen and PUF sponge (5% each), PLCs (4%), liquid pumps (3%), and others (2%). The operational cost comprised chemical cost (46%), pumping energy (42%), and sludge disposal (12%). The results revealed that the tank and heating costs accounted for the largest fraction of the total life cycle cost for full-scale An-HMBR. The heating cost can be compensated by gas recovery. Sensitivity analysis revealed that the interest rates, influent flow, and membrane flux were the most crucial parameters which affected the total cost of An-HMBR.

Metal ionic liquid-based hybrid membranes for ammonia separation through moderate interaction sites and cooperative transport channels

The combination ionic liquids (ILs) with membranes is a potential method for direct NH3 separation. In particular, ILs can modulate the interactions with NH3 and construct pathways in membranes for preferential NH3 transport, which is expected to overcome the trade-off effect and achieve a desirable separation performance. In this work, four metal ILs (MILs) with different metal centres and hydrogen bond donating ability, including [2-Mim][Li(NTf2)2], [Eim][Li(NTf2)2], [Bmim]2[Co(NCS)4], and [Bim]2[Co(NCS)4], were incorporated into sulfonated block copolymers to prepare MIL-based hybrid membranes for NH3 separation. The investigation of structure–performance relationships suggested that the interaction sites and transport channels could be tuned by the MIL type, which greatly affects the NH3 separation performance of the membranes. The Nexar/2-Mim-Li-10 membrane exhibits NH3 permeability of 735.6 Barrer with NH3/N2 selectivity of 844.5 and NH3/H2 selectivity of 154.7, which is higher than other MIL-based hybrid membranes owing to self-assembled transport channels and moderate complexation. Increasing the MIL content and feed pressure significantly improved NH3 separation performance.

Ion-Selective Transport Promotion Enabled by Angstrom-Scale Nanochannels in Dendrimer-Assembled Polyamide Nanofilm for Efficient Electrodialysis.

The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m-2 h-1 (K+), reaching excellent mono/multivalent selectivity up to 20.1 (K+/Mg2+) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.

Graphene oxide quantum dots-loaded sinomenine hydrochloride nanocomplexes for effective treatment of rheumatoid arthritis via inducing macrophage repolarization and arresting abnormal proliferation of fibroblast-like synoviocytes

The characteristic features of the rheumatoid arthritis (RA) microenvironment are synovial inflammation and hyperplasia. Therefore, there is a growing interest in developing a suitable therapeutic strategy for RA that targets the synovial macrophages and fibroblast-like synoviocytes (FLSs). In this study, we used graphene oxide quantum dots (GOQDs) for loading anti-arthritic sinomenine hydrochloride (SIN). By combining with hyaluronic acid (HA)-inserted hybrid membrane (RFM), we successfully constructed a new nanodrug system named HA@RFM@GP@SIN NPs for target therapy of inflammatory articular lesions. Mechanistic studies showed that this nanomedicine system was effective against RA by facilitating the transition of M1 to M2 macrophages and inhibiting the abnormal proliferation of FLSs in vitro. In vivo therapeutic potential investigation demonstrated its effects on macrophage polarization and synovial hyperplasia, ultimately preventing cartilage destruction and bone erosion in the preclinical models of adjuvant-induced arthritis and collagen-induced arthritis in rats. Metabolomics indicated that the anti-arthritic effects of HA@RFM@GP@SIN NPs were mainly associated with the regulation of steroid hormone biosynthesis, ovarian steroidogenesis, tryptophan metabolism, and tyrosine metabolism. More notably, transcriptomic analyses revealed that HA@RFM@GP@SIN NPs suppressed the cell cycle pathway while inducing the cell apoptosis pathway. Furthermore, protein validation revealed that HA@RFM@GP@SIN NPs disrupted the excessive growth of RAFLS by interfering with the PI3K/Akt/SGK/FoxO signaling cascade, resulting in a decline in cyclin B1 expression and the arrest of the G2 phase. Additionally, considering the favorable biocompatibility and biosafety, these multifunctional nanoparticles offer a promising therapeutic approach for patients with RA.Graphical abstract

Hybrid Membrane-Camouflaged Biomimetic Immunomodulatory Nanoturrets with Sequential Multidrug Release for Potentiating T Cell-Mediated Anticancer Immunity.

Ascorbic acid (AA) has been attracting great attention with its emerging potential in T cell-dependent antitumor immunity. However, premature blood clearance and immunologically "cold" tumors severely compromise its immunotherapeutic outcomes. As such, the reversal of the immunosuppressive tumor microenvironment (TME) has been the premise for improving the effectiveness of AA-based immunotherapy, which hinges upon advanced AA delivery and amplified immune-activating strategies. Herein, a novel Escherichia coli (E. coli) outer membrane vesicle (OMV)-red blood cell (RBC) hybrid membrane (ERm)-camouflaged immunomodulatory nanoturret is meticulously designed based on gating of an AA-immobilized metal-organic framework (MOF) onto bortezomib (BTZ)-loaded magnesium-doped mesoporous silica (MMS) nanovehicles, which can realize immune landscape remodeling by chemotherapy-assisted ascorbate-mediated immunotherapy (CAMIT). Once reaching the acidic TME, the acidity-sensitive MOF gatekeeper and MMS core within the nanoturret undergo stepwise degradation, allowing for tumor-selective sequential release of AA and BTZ. The released BTZ can evoke robust immunogenic cell death (ICD), synergistically promote dendritic cell (DC) maturation in combination with OMV, and ultimately increase T cell tumor infiltration together with Mg2+. The army of T cells is further activated by AA, exhibiting remarkable antitumor and antimetastasis performance. Moreover, the CD8-deficient mice model discloses the T cell-dependent immune mechanism of the AA-based CAMIT strategy. In addition to providing a multifunctional biomimetic hybrid nanovehicle, this study is also anticipated to establish a new immunomodulatory fortification strategy based on the multicomponent-driven nanoturret for highly efficient T cell-activation-enhanced synergistic AA immunotherapy.