Heterogeneous Membranes Research Articles

Processing of Sludge Water from Alumina Production by Electrodialysis

The possibility of using the electrodialysis for processing weak aluminate solutions (sludge water) for the purpose of their concentration and causticization is analyzed. For testing, a three-chamber electro-dialysis cell with heterogeneous cation exchange membranes MK-40 was used. The optimal operating parameters of the process were determined, as follows: pole-to-pole distance 3–4 cm and current density 2 A/dm2 at the operating voltage on the cell of 20–26 V. Specific electricity consumption was established as 9.7–20.6 kWh/kg alkali, causticization efficiency 56.1–69.6%, alkali yield – 81%.

Heterogeneous Covalent Organic Framework Membranes Mediated by Polycations for Efficient Ions Separation.

Precise ions sieving at angstrom-scale is gaining tremendous attention thanks to its significant impact at the water-energy nexus. Herein, a novel polycation-modulated interfacial polymerization (IP) strategy is developed to prepare a heterogeneously charged covalent organic frameworks (COFs) membrane. Cationic poly(diallyldimethylammonium chloride) (PDDA) regulates the growth and assembly of anionic COFs nanosheets, which thus provides a negative, smooth top surface and positive, rough bottom surface, indicating the presence of heterogeneously charged angstrom-scale channels through the membrane. Experiments and simulations are conducted to understand the facilitated ions transport behavior relative to specific interactions raised by heterogeneously charged channels and angstrom-scale steric hinderance as well, rendering the membrane with robust mono-/divalent cations sieving capabilities. The selectivity (61.6) of Li+ to Mg2+ in mixed saline under the continuous cross-flow filtration mode is superior to most of the reported nanofiltration membranes. This polycation-mediated interfacial polymerization strategy offers a compelling opportunity to develop versatile heterogeneously charged COF membranes for exquisite ion sieving.

Rational MOF Membrane Design for Gas Detection in Complex Environments.

Metal-organic frameworks (MOFs) hold significant promise in the realm of gas sensing. However, current understanding of their sensing mechanisms remains limited. Furthermore, the large-scale fabrication of MOFs is hampered by their inadequate mechanical properties. These two challenges contribute to the sluggish development of MOF-based gas-sensing materials. In this review, the selection of metal ions and organic ligands for designing MOFs is first presented, deepening the understanding of the interactions between different metal ions/organic ligands and target gases. Subsequently, the typical interfacial synthesis strategies (gas-solid, gas-liquid, solid-liquid interfaces) are provided, highlighting the potential for constructing MOF membranes on superhydrophobic and/or superhydrophilic substrates. Then, a multi-scale structure design strategies is proposed, including multi-dimensional membrane design and heterogeneous membrane design, to improve sensing performance through enhanced interfacial mass transfer and specific gas sieving. This strategy is anticipated to augment the task-specific capabilities of MOF-based materials in complex environments. Finally, several key future research directions are outlined with the aim not only to further investigate the underlying sensing principles of MOF membranes but also to achieve efficient detection of target gases amidst interfering gases and elevated moisture levels.

Impact of Asymmetric Microstructure on Ion Transport in Ti3C2Tx Membranes.

Consolidation or densification of low-dimensional MXene materials into membranes can result in the formation of asymmetric membrane structures. Nanostructural (short-range) and microstructural (long-range) heterogeneity can influence mass transport and separation mechanisms. Short-range structural dynamics include the presence of water confined between the 2D layers, while long-range structural properties include the formation of defects, micropores, and mesopores. Herein, it is demonstrated that structural heterogeneity in Ti3C2Tx membranes fabricated via vacuum-assisted filtration significantly affects ion transport. Higher ion permeabilities are achieved when the dense "bottom" side of the membrane, rather than the porous "top" side, faces the feed solution. Characterization of the membrane reveals distinct differences in flake alignment, surface roughness, and porosity across the membrane. The directional dependence on permeability suggests that one region of the membrane experiences stronger internal concentration polarization, potentially suppressing permeability through the porous side of the membrane.

Chlorophyll-Induced Lamellar to Nonlamellar Phase Transitions and Dynamical Heterogeneity in Plant Thylakoid Membranes.

Chlorophyll a (CLA) pigments and thylakoid membranes are crucial components of plants for photosynthesis. To understand the effect of CLA on the structure and dynamics of thylakoid membranes, coarse-grained molecular dynamics (CG MD) simulations of thylakoid membranes are performed by varying the numbers of CLA at 293 K using MARTINI-2 force fields. The membrane undergoes a lamellar to nonlamellar phase transition above a critical concentration of CLA. The CLAs dynamically form aggregates of different orders and preferentially fetch the least unsaturated nonbilayer-forming lipids around them, resulting in a nonlamellar phase with fused regions. These fused regions cause a structural arrest of CLA and lipids, inducing dynamic heterogeneity manifested by non-Gaussian parameters and van Hove correlation functions. The lamellar to nonlamellar phase transition of the membrane is associated with a drastic reduction in correlation length of the immobile CLA and lipids governed by the fused topology. Such insights into CLA-induced structural transitions in thylakoid membranes are pertinent for understanding nonphotochemical quenching mechanisms and hold promise for designing future artificial photosynthetic materials and applications in photodynamic therapy.

Nacre-inspired graphene oxide/polyethyleneimine-based ultra-thin heterogeneous superwetting membrane for highly stable separation of oil-in-water emulsions

Since the massive discharge of oily wastewater seriously affects both humans and natural development, the performance of conventional membrane materials in terms of interfacial stability and antifouling in the treatment of surfactant-containing emulsified oily wastewater is a major challenge. In this work, a novel nacre-inspired graphene oxide/polyethyleneimine-based ultra-thin chemically heterogeneous superwetting membrane was fabricated through vacuum-assisted self-assembly and post-modification methods for oil-in-water emulsion separation. The nacre-inspired heterogeneous membrane exhibited superhydrophilicity, underwater superoleophobicity (underwater oil contact angle was 157.7°), excellent crude oil adhesion resistance, high acid/alkaline stability, outstanding salt resistance, and good mechanical properties (Young’s modulus 1391.7 MPa). The heterogeneous membranes showed separation efficiencies of more than 99.9 % for a range of oil-in-water emulsions. The high-value membranes could achieve the permeances of 917–1256 L m−2h−1 bar−1 for pure water and 339.7–577 L m−2h−1 bar−1 for emulsion through a dead-end filter device, with the optimal long-term stable permeance only decreasing by 30.0 % compared to the initial value. After six test cycles, the membrane’s antifouling and self-cleaning properties were enhanced by constructing heterogeneous superwetting properties, and the flux recovery rate remained at 96.5 %. All of these results indicated that this method provides new ideas for the design and fabrication of highly stable and antifouling membrane materials.

Entangling roles of cholesterol-dependent interaction and cholesterol-mediated lipid phase heterogeneity in regulating listeriolysin O pore-formation.

Cholesterol-dependent cytolysins (CDCs) are the distinct class of β-barrel pore-forming toxins (β-PFTs) that attack eukaryotic cell membranes, and form large, oligomeric, transmembrane β-barrel pores. Listeriolysin O (LLO) is a prominent member in the CDC family. As documented for the other CDCs, membrane cholesterol is essential for the pore-forming functionality of LLO. However, it remains obscure how exactly cholesterol facilitates its pore formation. Here, we show that cholesterol promotes both membrane-binding and oligomerization of LLO. We demonstrate cholesterol not only facilitates membrane-binding, it also enhances the saturation threshold of LLO-membrane association, and alteration of the cholesterol-recognition motif in the LLO mutant (LLOT515G-L516G) compromises its pore-forming efficacy. Interestingly, such defect of LLOT515G-L516G could be rescued in the presence of higher membrane cholesterol levels, suggesting cholesterol can augment the pore-forming efficacy of LLO even in the absence of a direct toxin-cholesterol interaction. Furthermore, we find the membrane-binding and pore-forming abilities of LLOT515G-L516G, but not those of LLO, correlate with the cholesterol-dependent rigidity/ordering of the membrane lipid bilayer. Our data further suggest that the line tension derived from the lipid phase heterogeneity of the cholesterol-containing membranes could play a pivotal role in LLO function, particularly in the absence of cholesterol binding. Therefore, in addition to its receptor-like role, we conclude cholesterol can further facilitate the pore-forming, membrane-damaging functionality of LLO by asserting the optimal physicochemical environment in membranes. To the best of our knowledge, this aspect of the cholesterol-mediated regulation of the CDC mode of action has not been appreciated thus far.

Mixed dimensional assembly of biodegradable and antifouling wood-based covalent organic framework composite membranes for rapid and efficient dye/salt separation

Manipulating materials of different dimensions into heterogeneous nanofiltration membranes with unique physicochemical properties and molecular sieving channels provides an effective way for accurate and fast molecular separation. Here we introduce a heterogeneous structure hybrid connection strategy to fabricate biodegradable wood-based covalent organic framework (COF) composite membranes. As a proof of concept, 3D Picea jezoensis (Siebold & Zucc.) Carrière was selected as the substrate of the membrane and in situ growth of 2D iCOF selective layers. Effective modulation of iCOF layers by 1D sulfonated polyaryletherketone (SPEEK-Na) using the “needle and thread” method. The rearrangement of the above multidimensional materials formed charge-regulated properties of laminar nano-channels and smooth hydrophilic contact area, thereby endowing specific molecular transport pathways and sieving capability for efficient dye/salt separation under ultra-low pressure of 0.5 bar. The wood-based heterostructured membranes exhibited high dye rejection (>97 %), low salt rejection (<10 %), and high permeance (172.34 L m−2 h−1 bar−1), which is superior to many reported dye/salt separation membrane materials. In addition, the system exhibited a certain degree of operational stability, good antifouling, and soil biodegradability. Overall, this work enables the design and fabrication of heterostructured separation membranes to be obtained from nature and used in nature, resulting in efficient and sustainable water purification applications.

Transport and structural characteristics of heterogeneous ion-exchange membranes with varied dispersity of the ion exchanger

Transport and structural characteristics of heterogeneous ion-exchange membranes with varied dispersity of the ion exchanger

Raft-like lipid mixtures in the highly coarse-grained Cooke membrane model.

Lipid rafts are nanoscopic assemblies of sphingolipids, cholesterol, and specific membrane proteins. They are believed to underlie the experimentally observed lateral heterogeneity of eukaryotic plasma membranes and implicated in many cellular processes, such as signaling and trafficking. Ternary model membranes consisting of saturated lipids, unsaturated lipids, and cholesterol are common proxies because they exhibit phase coexistence between a liquid-ordered (lo) and liquid-disordered (ld) phase and an associated critical point. However, plasma membranes are also asymmetric in terms of lipid type, lipid abundance, leaflet tension, and corresponding cholesterol distribution, suggesting that rafts cannot be examined separately from questions about elasticity, curvature torques, and internal mechanical stresses. Unfortunately, it is challenging to capture this wide range of physical phenomenology in a single model that can access sufficiently long length- and time scales. Here we extend the highly coarse-grained Cooke model for lipids, which has been extensively characterized on the curvature-elastic front, to also represent raft-like lo/ld mixing thermodynamics. In particular, we capture the shape and tie lines of a coexistence region that narrows upon cholesterol addition, terminates at a critical point, and has coexisting phases that reflect key differences in membrane order and lipid packing. We furthermore examine elasticity and lipid diffusion for both phase separated and pure systems and how they change upon the addition of cholesterol. We anticipate that this model will enable significant insight into lo/ld phase separation and the associated question of lipid rafts for membranes that have compositionally distinct leaflets that are likely under differential stress-like the plasma membrane.

Mechanisms of electromagnetic field control on mineral scaling in brackish water reverse osmosis: Combined homogenous and heterogeneous nucleation

Electromagnetic field (EMF) treatment has emerged as a promising approach for scaling control due to its cost-effectiveness, simplicity, and low energy consumption. However, there is a limited understanding of the mechanisms by which applied EMF impacts mineral scaling in reverse osmosis (RO) systems. This has led to inconclusive and varied results and uncertainties regarding its effectiveness. This study elucidates the impacts of EMF on homogenous and heterogeneous nucleation and membrane performance during RO desalination of different feedwaters. Our results reveal that EMF exhibits greater efficacy in treating near-saturated water (SI∼0), especially when coupled with extended hydraulic flushing (HF). For saturated brackish water desalination, heterogeneous scaling predominantly occurs on membrane surfaces, with the effectiveness of EMF in inhibiting scaling primarily attributed to the hydration effect. In supersaturated solutions, EMF promotes bulk precipitation due to the magnetohydrodynamic effect, quickly blocking membrane pores. Thus, when the saturation reaches a certain high level during RO desalination, magnetohydrodynamic EMF effects can accelerate flux decline caused by homogeneous scaling. This work provides an efficient method for predicting EMF efficiency, emphasizing the importance of saturation conditions and HF cleaning duration in determining membrane performance, suggesting these show promise for improving undersaturated or near-saturated feedwater desalination via RO.

Interpreting effective energy barriers to membrane permeation in terms of a heterogeneous energy landscape

Major efforts in recent years have been directed towards understanding molecular transport in polymeric membranes, in particular reverse osmosis and nanofiltration membranes. Transition-state theory is an increasingly common approach to explore mechanisms of transmembrane permeation with molecular details, but most applications of this theory treat all free energy barriers to transport within the membrane as equal. This assumption neglects the inherent structural and chemical heterogeneity in polymeric membranes. In this work, we expand the transition-state theory framework to include distributions of membrane free energy barriers. Our mathematical framework is mechanism-agnostic, such that it generalizes to transport through any membrane for molecular separation. However, we focus our analysis on dense nanofiltration and reverse osmosis membranes. We show that the highest free energy barriers along the most permeable paths, rather than typical paths, provide the largest contributions to the experimentally-observed effective free energy barrier. We show that even moderate, random heterogeneity in molecular barriers will significantly impact how we interpret the mechanisms of transport through these membranes. Our study suggests that experimentally-measured barriers are not easily related to the underlying mechanisms governing transport, and simplified interpretations of these barriers will likely miss the mechanisms most relevant to the overall permeability.

Inorganic-organic hybrid heterogeneous membrane for zinc protective layers in high-performance aqueous zinc ion batteries

Aqueous zinc-ion Batteries (AZIBs) suffer from stability and performance limitations due to challenges related to the zinc (Zn) metal anode, including hydrogen evolution reaction (HER), metal corrosion, and Zn dendrite formation. To mitigate these issues, researchers are developing innovative coatings and protective layers for Zn anodes, focusing on enhancing ion conductivity, electrochemical inertness, mechanical strength, and processability. Hybrid organic-inorganic heterostructure coating materials with silver nanowires (Ag NWs) encapsulated with Polypyrrole (Ag/PPy) have shown promise in addressing these challenges. The Zn anode coated with Ag/PPy layers and paired with an α-MnO2 cathode, achieved an impressive initial capacity of 302 mAh/g at a current density of 0.5 A/g. Remarkably, it retained a substantial capacity of 283 mAh/g after 300 cycles at a current density of 0.5 A/g, demonstrating a 94 % capacity retention rate. Moreover, the symmetry cell using this anode maintains stable Zn deposition/stripping overpotentials even at a high current density (a rate of 10C) for over 175 h. These findings highlight the potential of Ag/PPy coatings as a viable approach for enhancing the surface chemistry and physical properties of the Zn metal anode, paving the way for a wider use of AZIBs.

Frontispiece: Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr‐MOF‐Based Heterogeneous Membrane with Trilayered Continuous Porous Structure

Frontispiece: Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr‐MOF‐Based Heterogeneous Membrane with Trilayered Continuous Porous Structure

Organelle-Targeted Laurdans Measure Heterogeneity in Subcellular Membranes and Their Responses to Saturated Lipid Stress.

Organelles feature characteristic lipid compositions that lead to differences in membrane properties. In cells, membrane ordering and fluidity are commonly measured using the solvatochromic dye Laurdan, whose fluorescence is sensitive to lipid packing. As a general lipophilic dye, Laurdan stains all hydrophobic environments in cells; therefore, it is challenging to characterize membrane properties in specific organelles or assess their responses to pharmacological treatments in intact cells. Here, we describe the synthesis and application of Laurdan-derived probes that read out the membrane packing of individual cellular organelles. The set of organelle-targeted Laurdans (OTL) localizes to the ER, mitochondria, lysosomes, and Golgi compartments with high specificity while retaining the spectral resolution needed to detect biological changes in membrane ordering. We show that ratiometric imaging with OTLs can resolve membrane heterogeneity within organelles as well as changes in lipid packing resulting from inhibition of trafficking or bioenergetic processes. We apply these probes to characterize organelle-specific responses to saturated lipid stress. While the ER and lysosomal membrane fluidity is sensitive to exogenous saturated fatty acids, that of mitochondrial membranes is protected. We then use differences in ER membrane fluidity to sort populations of cells based on their fatty acid diet, highlighting the ability of organelle-localized solvatochromic probes to distinguish between cells based on their metabolic state. These results expand the repertoire of targeted membrane probes and demonstrate their application in interrogating lipid dysregulation.

Heterogeneous acellular dermal matrix for wound repair after endoscopic Type-Ⅴa cordectomy

Objective:To observe the clinical effect of placing heterogeneous acellular dermal matrix membrane for laryngeal cavity wound healing after CO2 laser Type-Ⅴa cordectomy for glottic carcinoma. Methods:Thirty-five patients with bilateral vocal cord laryngeal cancer who underwent endoscopic CO2 laser surgery at the Department of Otorhinolaryngology Head and Neck Surgery, the Second Xiangya Hospital of Central South University from March 2018 to December 2019 were selected and divided into 2 groups, including 18 patients in the study group and 17 patients in the control group. The control group was simply placed silicone tube stent, while in the study group, heterogeneous acellular dermal matrix membrane was coated with silicone tube stent. The postoperative laryngeal wound repair and clinical manifestations were observed and compared between the two groups. Results:Compared postoperative laryngeal wound after 6 months: no patients in the study group had granulation tissue, whereas 4 patients in the control group had granulation tissue; 3 patients in the study group developed moderate to severe tissue adhesion, while 9 patients in the control group; 10 patients in the control group developed 2nd to 4th degree laryngeal obstruction, compared with only 4 patients in the study group. Conclusion:The primary placement of ADM can reduce laryngeal granulation tissue and tissue adhesion after CO2 laser Type-Ⅴa cordectomy for laryngeal cancer, and may reduce the occurrence of postoperative laryngeal obstruction.

Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr‐MOF‐Based Heterogeneous Membrane with Trilayered Continuous Porous Structure

AbstractDesigning a nanofluidic membrane with high selectivity and fast ion transport property is the key towards high‐performance osmotic energy conversion. However, most of reported membranes can produce power density less than commercial benchmark (5 W/m2), due to the imbalance between ion selectivity and permeability. Here, we report a novel nanoarchitectured design of a heterogeneous membrane with an ultrathin and dense zirconium‐based UiO‐66‐NH2 metal–organic framework (MOF) layer and a highly aligned and interconnected branched alumina nanochannel membrane. The design leads to a continuous trilayered pore structure of large geometry gradient in the sequence from angstrom‐scale to nano‐scale to sub‐microscale, which enables the enhanced directional ion transport, and the angstrom‐sized (~6.6–7 Å) UiO‐66‐NH2 windows render the membrane with high ion selectivity. Consequently, the novel heterogeneous membrane can achieve a high‐performance power of ~8 W/m2 by mixing synthetic seawater and river water. The power density can be largely upgraded to an ultrahigh ~17.1 W/m2 along with ~48.5 % conversion efficiency at a 50‐fold KCl gradient. This work not only presents a new membrane design approach but also showcases the great potential of employing the zirconium‐based MOF channels as ion‐channel‐mimetic membranes for highly efficient blue energy harvesting.

Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr-MOF-Based Heterogeneous Membrane with Trilayered Continuous Porous Structure.

Designing a nanofluidic membrane with high selectivity and fast ion transport property is the key towards high-performance osmotic energy conversion. However, most of reported membranes can produce power density less than commercial benchmark (5 W/m2), due to the imbalance between ion selectivity and permeability. Here, we report a novel nanoarchitectured design of a heterogeneous membrane with an ultrathin and dense zirconium-based UiO-66-NH2 metal-organic framework (MOF) layer and a highly aligned and interconnected branched alumina nanochannel membrane. The design leads to a continuous trilayered pore structure of large geometry gradient in the sequence from angstrom-scale to nano-scale to sub-microscale, which enables the enhanced directional ion transport, and the angstrom-sized (~6.6-7 Å) UiO-66-NH2 windows render the membrane with high ion selectivity. Consequently, the novel heterogeneous membrane can achieve a high-performance power of ~8 W/m2 by mixing synthetic seawater and river water. The power density can be largely upgraded to an ultrahigh ~17.1 W/m2 along with ~48.5 % conversion efficiency at a 50-fold KCl gradient. This work not only presents a new membrane design approach but also showcases the great potential of employing the zirconium-based MOF channels as ion-channel-mimetic membranes for highly efficient blue energy harvesting.

Light-Powered Directional Ion Transport via PFN-Br/MoS2 Heterogeneous Membranes: Band Alignment and Activation Energy Barrier Engineering.

Biological photoresponsive ion transport systems consistently attract researchers' attention owing to their remarkable functions of harvesting energy from nature and participating in visual perception systems. Designing and constructing artificial light-driven ion transport devices to mimic biological counterparts remains a challenge owing to fabrication limitations in nanoconfined spaces. Herein, a typical conjugated polyelectrolyte (PFN-Br) was assembled onto a laminated MoS2M using simple solution-processing vacuum filtration, resulting in a heterogeneous three- and two-dimensional nanoporous membrane. The designed band alignment between PFN-Br and MoS2 enables effective directional ion transport under irradiation in an equilibrium solution, even against a 30-fold concentration gradient. The staggered energy structure of PFN-Br and MoS2 enhances charge separation and establishes a photogenerated potential as the driving force for ion transport. Additionally, the activation energy barrier for ion transport across the heterogeneous membrane decreased by 60% after light irradiation, considerably improving ion transport flux. The easy fabrication and high performance of the membrane in light-powered ion transport provide promising approaches for designing nanofluidic devices with possible applications in energy conversion, light-enhanced biosensing, and photoresponsive ionic devices.

Chitosan hybrid nanomaterials: A study on interaction with biomimetic membranes

This study examined the influence of nanomaterials (NMs) on the organization of membrane lipids and the resulting morphological changes. The cell plasma membrane is heterogeneous, featuring specialized lipid domains in the liquid-ordered (Lo) phase surrounded by regions in the liquid-disordered (Ld) phase. We utilized model membranes composed of various lipids and lipid mixtures in different phase states to investigate the interactions between the NMs and membrane lipids. Specifically, we explored the interactions of pure chitosan (CS) and CS-modified nanocomposites (NCs) with ZnO, CuO, and SiO2 with four lipid mixtures: egg-phosphatidylcholine (EggPC), egg-sphingomyelin/cholesterol (EggSM/Chol), EggPC/Chol, and EggPC/EggSM/Chol, which represent the coexistence of Ld, Lo, and Ld/Lo, respectively. The data show that CS NMs increase the membrane lipid order at glycerol level probed by Laurdan spectroscopy. Additionally, the interaction of CS-based NMs with membranes leads to an increase in bending elasticity modulus, zeta potential, and vesicle size. The lipid order changes are most significant in the highly fluid Ld phase, followed by the Lo/Ld coexistence phase, and are less pronounced in the tightly packed Lo phase. CS NMs induced egg PC vesicle adhesion, fusion, and shrinking. In heterogeneous Lo/Ld membranes, inward invaginations and vesicle shrinking via the Ld phase were observed. These findings highlight mechanisms involved in CS NM-lipid interactions in membranes that mimic plasma membrane heterogeneity.