Mixed matrix membranes (MMMs) constitute a type of molecular separation membranes in which a nanomaterial type filler is dispersed in a given polymer to enhance its selective permeation ability. The key issue in MMMs is the establishing of a proper filler-polymer interaction to avoid non-selective transport paths while increasing permeability but also to improve other membrane properties such as aging and plasticization. Along the pass years several strategies have been applied to enhance the physicochemical interaction between the fillers (e.g. silicas, zeolites, porous coordination polymers, carbonaceous materials, etc.) and the membrane polymers: increase of external surface area, priming, use of intrinsically more compatible fillers, in situ synthesis of filler, in situ polymerization, polymer side-chain modification and post-synthetic modification of filler.

Nasopharyngeal cancer (NPC) is a malignant tumor with high prevalence in Southeast Asia and highly invasive and metastatic characteristics. Radiotherapy is the primary strategy for NPC treatment, however there is still lack of effect method for predicting the radioresistance that is the main reason for treatment failure. Herein, the molecular profiles of patient plasma from NPC with radiotherapy sensitivity and resistance groups as well as healthy group, respectively, were explored by label-free surface enhanced Raman spectroscopy (SERS) based on surface plasmon resonance for the first time. Especially, the components with different molecular weight sizes were analyzed via the separation process, helping to avoid the possible missing of diagnostic information due to the competitive adsorption. Following that, robust machine learning algorithm based on principal component analysis and linear discriminant analysis (PCA-LDA) was employed to extract the feature of blood-SERS data and establish an effective predictive model with the accuracy of 96.7% for identifying the radiotherapy resistance subjects from sensitivity ones, and 100% for identifying the NPC subjects from healthy ones. This work demonstrates the potential of molecular separation-assisted label-free SERS combined with machine learning for NPC screening and treatment strategy guidance in clinical scenario.

The selective separation of small molecules at the sub-nanometer scale has broad application prospects in the field, such as energy, catalysis, and separation. Conventional polymeric membrane materials (e.g., nanofiltration membranes) for sub-nanometer scale separations face challenges, such as inhomogeneous channel sizes and unstable pore structures. Combining polymers with metal-organic frameworks (MOFs), which possess uniform and intrinsic pore structures, may overcome this limitation. This combination has resulted in three distinct types of membranes: MOF polycrystalline membranes, mixed-matrix membranes (MMMs), and thin-film nanocomposite (TFN) membranes. However, their effectiveness is hindered by the limited regulation of the surface properties and growth of MOFs and their poor interfacial compatibility. The main issues in preparing MOF polycrystalline membranes are the uncontrollable growth of MOFs and the poor adhesion between MOFs and the substrate. Here, polymers could serve as a simple and precise tool for regulating the growth and surface functionalities of MOFs while enhancing their adhesion to the substrate. For MOF mixed-matrix membranes, the primary challenge is the poor interfacial compatibility between polymers and MOFs. Strategies for the mutual modification of MOFs and polymers to enhance their interfacial compatibility are introduced. For TFN membranes, the challenges include the difficulty in controlling the growth of the polymer selective layer and the performance limitations caused by the \"trade-off\" effect. MOFs can modulate the formation process of the polymer selective layer and establish transport channels within the polymer matrix to overcome the \"trade-off\" effect limitations. This review focuses on the mechanisms of synergistic construction of polymer-MOF membranes and their structure-nanofiltration performance relationships, which have not been sufficiently addressed in the past.

Supramolecular assembly frameworks (SAFs) represent a new category of porous materials, utilizing non-covalent interactions, setting them apart from metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). This category includes but is not restricted to hydrogen-bonded organic frameworks and supramolecular organic frameworks. SAFs stand out for their outstanding porosity, crystallinity, and stability, alongside unique dissolution-recrystallization dynamics that enable significant structural and functional modifications. Crucially, their non-covalent assembly strategies allow for a balanced manipulation of porosity, symmetry, crystallinity, and dimensions, facilitating the creation of advanced crystalline porous materials unattainable through conventional covalent or coordination bond synthesis. Despite their considerable promise in overcoming several limitations inherent to MOFs and COFs, particularly in terms of solution-processability, SAFs have received relatively little attention in recent literature. This Minireview aims to shed light on standout SAFs, exploring their design principles, synthesis strategies, and characterization methods. It emphasizes their distinctive features and the broad spectrum of potential applications across various domains, aiming to catalyze further development and practical application within the scientific community.

Crystalline porous metal-organic materials are ideal building blocks for separation membranes because of their molecular-sized pores and highly ordered pore structure. However, creating ultrathin, defect-free crystalline membranes is challenging due to inevitable grain boundaries. Herein, we reported an amorphous metal-organic hybrid (MOH) membrane with controlled microporosity. The synthesis of the MOH membrane entails the use of titanium alkoxide and organic linkers containing di/multicarboxyl groups as monomers in the polymerization reaction. The resultant membranes exhibit similar microporosity to existing molecular sieve materials and high chemical stability against harsh chemical environments owing to the formation of stable Ti-O bonds between metal centers and organic linkers. An interfacial polymerization is developed to fabricate an ultrathin MOH membrane (thickness of the membrane down to 80 nm), which exhibits excellent rejections (>98% for dyes with molecular weights larger than 690 Da) and high water permeance (55 L m-2 h-1 bar-1). The membranes also demonstrate good flexibility, which greatly improves the processability of the membrane materials.

Azobenzene, which activates its geometric and chemical structure under light stimulation enables noninvasive control of mass transport in many processes including membrane separations. However, producing azobenzene-decorated channels that have precise size tunability and favorable pore wall chemistry allowing fast and durable permeation to solvent molecules, remains a great challenge. Herein, an advanced membrane that comprises geometry and polarity gradients within covalent organic framework (COF) nanochannels utilizing photoisomerization of azobenzene groups is reported. Such functional variations afford reduced interfacial transfer resistance and enhanced solvent-philic pore channels, thus creating a fast solvent transport pathway without compromising selectivity. Moreover, the membrane sets up a densely covered defense layer to prevent foulant adhesion and the accumulation of cake layer, contributing to enhanced antifouling resistance to organic foulants, and a high recovery rate of solvent permeance. More importantly, the solvent permeance displays a negligible decline throughout the long-term filtration for over 40 days. This work reports the geometry and polarity gradients in COF channels induced by the conformation change of branched azobenzene groups and demonstrates the strong capability of this conformation change in realizing fast and durable molecular separations.

Two-dimensional materials are widely used in membrane separation, but the loose distribution and severe expansion between graphene oxide (GO) nanosheets limit its application. Here, we introduce a two-dimensional MOF material into the GO membrane to enhance its water permeance and separation performance. The MOF/GO composite membrane was prepared by vacuum filtration. The MOF and GO nanosheets were tightly stacked through the π-π effect, and the shortened transmission path and enhanced pore structure greatly improved the water permeance of the composite membrane. The MOF/GO membrane exhibited a high water permeance of 56.94 L m-2 h-1 bar-1. The rejection rates of methylene blue and was as methyl orange dyes were as high as 99.79% and 99.11%, respectively. At increased dye concentration, the rejection rate of methylene blue was still maintained greater than 99%. Dye rejection after 18 h of continuous operation remains above 90%. This work provides new ideas for improving membrane separation materials. The combination of two-dimensional heterogeneous materials can result in synergistic advantages for the development of composite membranes with high water permeance and high rejection rate.

Nanosheets derived from two-dimensional covalent organic frameworks (2D COFs) are increasingly desirable in various fields. While breakthroughs in the chemical and physical delamination of 2D COFs are rising, precisely regulating the growth of the COF nanosheets has not been realized yet. Herein, we report an effective strategy of polymer-manipulated crystallization to accurately control the growth of COF nanosheets. Chemically asymmetric polyvinylpyrrolidone (PVP) is developed as the manipulator that selectively interacts with the aldehydes and (100) facet to induce anisotropic growth of COFs. The number of PVP constitutional units determines this specific interaction, leading to molecularly thin but thickness-controllable nanosheets with excellent dispersity. We process these nanosheets into robust A4-sized membranes for ultraselective molecular separation. The membrane intercalated with long-chain PVP demonstrates largely improved performance, surpassing the reported COF membranes. This work reports a strategy for anisotropically crystallizing 2D COFs to yield processable nanosheets toward practical applications.

Molecular separations involving solvents and organic impurities represent great challenges for environmental and water-intensive industries. Novel materials with intrinsic nanoscale pores offer a great choice for improvement in terms of energy efficiency and capital costs. Particularly, in applications where gradient and ordered separation of organic contaminants remain elusive, smart materials with switchable pores can offer efficient solutions. Here, we report a hierarchically networked porous organic cage membrane with dynamic control over pores, elucidating stable solvent permeance and tunable dye rejection over different molecular weights. The engineered cage membrane can spontaneously modulate its geometry and pore size from water to methanol and DMF in a reversible manner. The cage membrane exhibits ≥585.59 g mol-1 molecular weight cutoff preferentially in water and is impeded by methanol (799.8 g mol-1) and DMF (≈1017 g mol-1), reflecting 36 and 73% change in rejection due to self-regulation and the flexible network, respectively. Grazing incidence X-ray diffraction illustrates a clear peak downshift, suggesting an intrinsic structural change when the cage membranes were immersed in methanol or DMF. We have observed reversible structural changes that can also be tuned by preparing a methanol/DMF mixture and adjusting their ratio, thereby enabling gradient molecular filtration. We anticipate that such cage membranes with dynamic selectivity could be promising particularly for industrial separations and wastewater treatment.

Self-assembled graphene oxide lyotropic liquid crystal (GO LLC) structures are mostly formed in aqueous medium; however, most GO derivatives are water insoluble, so processing GO LLCs in water poses a practical limitation. The use of polar aprotic solvent (like dimethyl sulfoxide) for the formation of GO LLC structures would be interesting, because it would allow incorporating additives, like photoinitiators or cross-linkers, or blending with polymers that are insoluble in water, which hence would expand its scope. The well-balanced electrostatic interaction between DMSO and GO can promote and stabilize the GO nanosheets\' alignment even at lower concentrations. With this in mind, herein we report mechanically robust, chlorine-tolerant, self-assembled nanostructured GO membranes for precise molecular sieving. Small-angle X-ray scattering and polarized optical microscopy confirmed the alignment of the modified GO nanosheets in polar aprotic solvent, and the LLC structure was effectively preserved even after cross-linking under UV light. We found that the modified GO membranes exhibited considerably improved salt rejection for monovalent ions (99%) and water flux (120 LMH) as compared to the shear-aligned GO membrane, which is well supported by forward osmosis simulation studies. Additionally, our simulation studies indicated that water molecules traveled a longer path while permeating through the GO membrane compared to the GO LLC membrane. Consequently, salt ions permeate slowly across the GO LLC membrane, yielding higher salt rejection than the GO membrane. This begins to suggest strong electrostatic repulsion with the salt ions, causing higher salt rejection in the GO LLC membrane. We foresee that the ordered cross-linked GO sheets contributed to excellent mechanical stability under a high-pressure, cross-flow, chlorine environment. Overall, these membranes are easily scalable, exhibit good mechanical stability, and represent a breakthrough for the potential use of polymerized GO LLC membranes in practical water remediation applications.