Synergistic Construction of Sub-Nanometer Channel Membranes through MOF-Polymer Composites: Strategies and Nanofiltration Applications.

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.

Conductive nanofiltration membranes via in situ PEDOT-polymerization for electro-assisted membrane fouling mitigation.

Nanofiltration (NF) membranes play a pivotal role in water treatment; however, the persistent challenge of membrane fouling hampers their stable application. This study introduces a novel approach to address this issue through the creation of a poly(3,4-ethylenedioxythiophene) (PEDOT)-based conductive membrane, achieved by synergistically coupling interfacial polymerization (IP) with in situ self-polymerization of EDOT. During the IP reaction, the concurrent generation of HCl triggers the protonation of EDOT, activating its self-polymerization into PEDOT. This interwoven structure integrates with the polyamide network to establish a stable selective layer, yielding a remarkable 90 % increase in permeability to 20.4 L m-2 h-1 bar-1. Leveraging the conductivity conferred by PEDOT doping, an electro-assisted cleaning strategy is devised, rapidly restoring the flux to 98.3 % within 5 min, outperforming the 30-minute pure water cleaning approach. Through simulations in an 8040 spiral-wound module and the utilization of the permeated salt solution for cleaning, the electro-assisted cleaning strategy emerges as an eco-friendly solution, significantly reducing water consumption and incurring only a marginal electricity cost of 0.055 $ per day. This work presents an innovative avenue for constructing conductive membranes and introduces an efficient and cost-effective electro-assisted cleaning strategy to effectively combat membrane fouling.

Locking Patterned Carbon Nanotube Cages by Nanofibrous Mats to Construct Cucurbituril[n]-Based Ultrapermselective Dye/Salt Separation Membranes.

Surface patterning is a promising strategy to overcome the trade-off effect of separation membranes. Herein, a bottom-up patterning strategy of locking micron-sized carbon nanotube cages (CNCs) onto a nanofibrous substrate is developed. The strongly enhanced capillary force triggered by the abundant narrow channels in CNCs endows the precisely patterned substrate with excellent wettability and antigravity water transport. Both are crucial for the preloading of cucurbit[n]uril (CB6)-embeded amine solution to form an ultrathin (∼20 nm) polyamide selective layer clinging to CNCs-patterned substrate. The CNCs-patterning and CB6 modification result in a 40.2% increased transmission area, a reduced thickness, and a lowered cross-linking degree of selective layer, leading to a high water permeability of 124.9 L·m-2 h-1 bar-1 and a rejection of 99.9% for Janus Green B (511.07 Da), an order of magnitude higher than that of commercial membranes. The new patterning strategy provides technical and theoretical guidance for designing next-generation dye/salt separation membranes.

Roles and gains of coordination chemistry in nanofiltration membrane: A review.

The nanofiltration (NF) membranes with the specific separation accuracy for molecules with the size of 0.5-2 nm have been applied in various industries. However, the traditional polymeric NF membranes still face problems like the trade-off effect, organic solvent consumption, and weak durability in harsh conditions. The participation of coordination action or metal-organic coordination compounds (MOCs) brings the membrane with uniform pores, better antifouling properties, and high hydrophilicity. Some of the aqueous-phase reactions also help to introduce a green fabrication process to NF membranes. This review critically summarizes the recent research progress in coordination chemistry relevant NF membranes. The participation of coordination chemistry was classified by the various functions in NF membranes like additives, interlayers, selective layers, coating layers, and cross-linkers. Then, the effect and mechanism of the coordination chemistry on the performance of NF membranes are discussed in depth. Perspectives are given for the further promotion that coordination chemistry can make in NF processes. This review also provides comprehensive insight and constructive guidance on high-performance NF membranes with coordination chemistry.

Removing miscellaneous heavy metals by all-in-one ion exchange-nanofiltration membrane.

The composition of wastewater containing heavy metal mixtures is often complex and poses a serious threat to human and environmental health. Effective removal of a variety of heavy metal ions with a single technology is challenging, and the conventional split integrated technologies require multi-step processing and a massive footprint. For the first time, we achieve hierarchically integrating ion exchange and nanofiltration into all-in-one "iNF" membranes. The iNF membrane has a hierarchical structure with an interfacial polymerization layer and an ion exchange layer, which can achieve highly efficient indiscriminate heavy metal ion removal, overcoming the defect that traditional nanofiltration membranes can only remove single metal cations or oxyanions. The ion exchange layer can remove heavy metal ions through sulfonic acid groups and quaternary amine groups. In addition, the ion exchange layer can be regenerated by electro-deionization, which is meaningful for sustainable membrane usage. This facile, scalable, and compact integrated process shows outstanding potential and universal applicability in complex wastewater treatment.

Voltage-Gated Membranes Incorporating Cucurbit[n]uril Molecular Containers for Molecular Nanofiltration.

Smart voltage-gated nanofiltration membranes have enormous potential for on-demand and precise separation of similar molecules, which is an essential element of sustainable water purification and resource recovery. However, the existing voltage-gated membranes are hampered by limited selectivity, stability, and scalability due to electroactive monomer dimerization. Here, for the first time, the host-guest recognition properties of cucurbit[7]uril (CB[7]) are used to protect the viologen derivatives and promote their assembly into the membrane by interfacial polymerization. Viologen functions as a voltage switch, whereas CB[7] complexation prevents its dimerization and improves its redox stability. The inhibited diffusion of the CB[7]-viologen complex enables the precise patterning of the surface structure. The resultant voltage-gated membrane displays 80% improved rejection performance, excellent recovery accuracy for similar molecules, and anti-fouling properties. This work not only provides an innovative strategy for the preparation of voltage-gated smart nanofiltration membranes but also opens up new avenues for ion-selective transmission in water treatment, bionic ion channels, and energy conversion.

Encapsulated Polyethyleneimine Enables Synchronous Nanostructure Construction and In Situ Functionalization of Nanofiltration Membranes.

Highly permselective nanostructured membranes are desirable for the energy-efficient molecular sieving on the subnanometer scale. The nanostructure construction and charge functionalization of the membranes are generally carried out step by step through the conventional layer-by-layer coating strategy, which inevitably brings about a demanding contradiction between the permselective performance and process efficiency. For the first time, we report the concurrent construction of the well-defined molecular sieving architectures and tunable surface charges of nanofiltration membranes through precisely controlled release of the nanocapsule decorated polyethyleneimine and carbon dioxide. This novel strategy not only substantially shortens the fabrication process but also leads to impressive performance (permeance up to 37.4 L m-2 h-1 bar-1 together with a rejection 98.7% for Janus Green B-511 Da) that outperforms most state-of-art nanofiltration membranes. This study unlocks new avenues to engineer next-generation molecular sieving materials simply, precisely, and cost efficiently.

Precisely Patterned Nanostrand Surface of Cucurbituril[n]-Based Nanofiltration Membranes for Effective Alcohol-Water Condensation.

Low concentration alcohols produced by state-of-the-art biological fermentation restrict subsequent purification processes for chemical, pharmaceutical, biofuel, and other applications. Herein, a rarely reported cucurbituril[n] (n = 6, 8) is employed to pattern the thin-film composite membranes with controllable and quantifiable nanostrand structures through a host-guest strategy. The resulting nanofiltration membrane with such morphology is the first report that exhibits excellent separation performance for isopropyl alcohol (IPA) and water, condensing the initial 0.5 wt % IPA aqueous solution to 9.0 wt %. This not only provides a novel strategy for patterning nanostructural morphology but also makes nanofiltration membranes promising for alcohol condensation in the biological fermentation industry that may reduce energy consumption and postprocessing costs.

Self-Cleaning Nanofiltration Membranes by Coordinated Regulation of Carbon Quantum Dots and Polydopamine.

Performance declination of nanofiltration (NF) membranes caused by concentration polarization (CP) and membrane fouling has severely restricted their practical application in many fields. This work reports the construction of a novel interlayer between the substrate and the selective layer of conventional composite membranes by coordinating regulation of carbon quantum dots (CQDs) and polydopamine (PDA). Unlike traditional methods that treat CP and fouling separately, the new strategy grants the membrane with dual functions at one time. First, the insertion of the PDA-CQDs layer reformulates the interfacial polymerization process that reduces the solute transport resistance and mitigates the CP issue. Second, the sandwiched photoactive CQDs can degrade organic molecules adsorbed on the membrane surface under visible light, which is promising for low-cost fouling remediation. This study may offer valuable insights into the preparation of durable self-cleaning NF membranes for the effective treatment of complex wastewater in various industries.

Continuous flow knitting of a triptycene hypercrosslinked polymer.

By replacing Lewis acids with Brønsted acids as catalysts, continuous flow synthesis of hypercrosslinked polymers is achieved within 10% of the time required for a typical batch reaction. Compared with batch-synthesised polymers, the flow-produced materials take up 24% more CO2, precluding the need for lengthy reaction protocols to yield high-performance hypercrosslinked polymers for carbon capture.

Prognostic role of PIK3CA mutations and their association with hormone receptor expression in breast cancer: a meta-analysis.

The phosphatidylinositol-4, 5-bisphosphate 3-kinase, catalytic subunit alpha (PIK3CA) gene is frequently mutated in breast cancer (BCa). Sex hormone receptors (HRs), including estrogen receptor (ER) and progesterone receptor (PR) play pivotal roles in BCa. In this study, we evaluated the association between PIK3CA mutations and ER/PR expression and the prognostic role of PIK3CA mutations in BCa patients, and in particular, HR-positive BCa. Thirty-two studies involving 5719 cases of BCa obtained from database searches were examined. PIK3CA gene mutations correlated significantly with ER/PR expression (p < 0.00001) and relapse-free survival (RFS) (hazard ratio [HR] 0.76, 95% confidence interval [CI] 0.59-0.98, p = 0.03) but not overall survival (OS) (HR 1.14, 95%CI 0.72-1.82, p = 0.57) in unsorted BCa patients. PIK3CA mutations were not associated with OS (HR 1.06, 95%CI 0.67-1.67, p = 0.81) or RFS (HR 0.86, 95%CI 0.53-1.40, p = 0.55) in HR-positive BCa patients. In conclusion, PIK3CA mutations were significantly related to ER/PR expression and RFS in unsorted BCa patients. However, the clinical implications of PIK3CA mutations may vary according to different mutant exons. And PIK3CA mutations alone may have limited prognostic value for HR-positive BCa patients.

Chelating polymer modified P84 nanofiltration (NF) hollow fiber membranes for high efficient heavy metal removal.

High performance nanofiltration (NF) membranes for heavy metal removal have been molecularly designed by adsorption of chelating polymers containing negatively charged functional groups such as poly (acrylic acid-co-maleic acid) (PAM), poly (acrylic acid) (PAA) and poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine) (PDMED) on the positively charged polyethyleneimine (PEI) cross-linked P84 hollow fiber substrates. Not only do these chelating polymers change the membrane surface charge and pore size, but also provide an extra mean to remove heavy metal ions through adsorption in addition to traditional steric effect and Donnan exclusion. The adsorbed membranes have comparable water permeability and superior rejections to heavy metals, for instance, Pb(NO3)2, CuSO4, NiCl2, CdCl2, ZnCl2, Na2Cr2O7 and Na2HAsO4, with rejections higher than 98%. The membranes also display excellent rejections to mixed ions with rejections more than 99%. The newly developed membranes show reasonably stability during 60-h tests as well as multiple washes.

A single nucleotide polymorphism in PIK3CA gene is inversely associated with P53 protein expression in breast cancer.

Single nucleotide polymorphism (SNP) rs17849071 was recently reported to be inversely associated with PIK3CA amplification in follicular thyroid cancer, but the main function of this SNP remains unclear. In this study, by using PCR and sequencing method, we explored whether this SNP was associated with P53 expression status and other clinicopathological characteristics in 62 Chinese breast cancer (BCa) patients. In our results, P53 protein accumulation was significantly associated with HER2 overexpression (P = 0.013) and Ki-67 expression (P = 0.007), which were in accord with previous studies. Besides, there was a significantly inverse relationship between P53 protein expression and rs17849071 GT+GG genotype in Chinese BCa patients (P = 0.044). The SNP was not related to other important BCa markers such as estrogen receptor, progestin receptor, and HER2. Among different BCa intrinsic subtypes, no significant differences were found on P53 expression status (P = 0.356) or rs17849071 polymorphism (T>G) (P = 0.813). In conclusion, SNP rs17849071 GT+GG genotype was inversely associated with P53 protein accumulation in BCa samples. Studies with larger sample size focusing on exploring the relationship of rs17849071 polymorphisms, P53 accumulation, P53 mutations, and PIK3CA amplification might be needed.

Outer-selective pressure-retarded osmosis hollow fiber membranes from vacuum-assisted interfacial polymerization for osmotic power generation.

In this paper, we report the technical breakthroughs to synthesize outer-selective thin-film composite (TFC) hollow fiber membranes, which is in an urgent need for osmotic power generation with the pressure-retarded osmosis (PRO) process. In the first step, a defect-free thin-film composite membrane module is achieved by vacuum-assisted interfacial polymerization. The PRO performance is further enhanced by optimizing the support in terms of pore size and mechanical strength and the TFC layer with polydopamine coating and molecular engineering of the interfacial polymerization solution. The newly developed membranes can stand over 20 bar with a peak power density of 7.63 W/m(2), which is equivalent to 13.72 W/m(2) of its inner-selective hollow fiber counterpart with the same module size, packing density, and fiber dimensions. The study may provide insightful guidelines for optimizing the interfacial polymerization procedures and scaling up of the outer-selective TFC hollow fiber membrane modules for PRO power generation.

Hyperbranched polyethyleneimine induced cross-linking of polyamide-imide nanofiltration hollow fiber membranes for effective removal of ciprofloxacin.

This study aims to develop a positively charged nanofiltration (NF) hollow fiber membrane for effective removal of ciprofloxacin from water. A novel NF membrane was fabricated by hyperbranched polyethyleneimine (PEI) induced cross-linking on a polyamide-imide hollow fiber support. The spongy-like, fully porous membrane support provides minimal transport resistance and sufficient mechanical strengths for water permeation under high pressures. It is found that the PEI modification significantly influences NF performance through the mechanisms of size exclusion, charge repulsion, and solute-membrane affinity. Specifically, after PEI induced cross-linking, the membrane pore size is significantly reduced. The membrane surface becomes more hydrophilic and positively charged. As a result of these synergic effects, the rejection of ciprofloxacin is substantially enhanced. Furthermore, experimental results show that the molecular weight of PEI has tremendous effect on NF performance of the as-modified membrane. The NF membrane modified by a high molecular weight PEI_60K exhibits the highest rejection, the lowest fouling tendency, and keeps a constant flux over the whole pH range. This study may have great potential for developing high-performance antifouling NF hollow fiber membranes for various industrial applications.

Silencing PinX1 compromises telomere length maintenance as well as tumorigenicity in telomerase-positive human cancer cells.

The nucleolar protein PinX1 has been proposed to be a putative tumor suppressor due to its binding to and inhibition of the catalytic activity of telomerase, an enzyme that is highly expressed in most human cancers in which it counteracts telomere shortening-induced senescence to confer cancer cell immortalization. However, the role of PinX1 in telomere regulation, as well as in cancer, is still poorly understood. In this study, we showed that the PinX1 protein is constitutively expressed in various human cells regardless of their telomerase activity and malignant status. Most interestingly, we found that silencing PinX1 expression by a potent short hairpin RNA construct led to a robust telomere length shortening and growth inhibition in telomerase-positive but not in telomerase-negative human cancer cells. We further showed that silencing PinX1 significantly reduced the endogenous association of telomerase with the Pot1-containing telomeric protein complex, and therefore, could account for the phenotypic telomere shortening in the affected telomerase-positive cancer cells. Our results thus reveal a novel positive role for PinX1 in telomerase/telomere regulations and suggest that the constitutive expression of PinX1 attributes to telomere maintenance by telomerase and tumorigenicity in cancer cells.