Selective Transport Mechanism Research Articles

Advanced membrane contactor coupled with electrodialysis metathesis for efficient carbon dioxide capture and waste salt remediation

Rapid development of society has led to significant increases in carbon dioxide (CO2) emissions, primarily driven by intensified industrial activities and urbanization. Capture and utilization of CO2 not only mitigate greenhouse gas emissions but also support the transition towards a circular economy by recycling CO2 into high-value products. This study proposed a membrane contactor and electrodialysis metathesis (MC-EDM) for CO2 capture, NH4HCO3 generation, and NaHCO3 conversion. The MC facilitated the selective capture of CO2 from gas streams. Concurrently, EDM enhanced the NaHCO3/NH4Cl conversion from NH4HCO3/NaCl through selective ion transport mechanisms. The key influencing factors (e.g., gas flow rate, liquid flow rate, and ammonia concentration) for the MC process were optimized to achieve 1.014 mol/L NH4HCO3 concentration with 88.73 % yield and 78.94 % CO2 removal efficiency. Moreover, the parameters (e.g., solid-liquid ratio, membrane type, operating voltage, and salt component ratio) for the EDM process were optimized to achieve NaHCO3 with a 90.9 % yield and 97.80 % purity. Economic analysis indicated the overall process for NaHCO3 recovery was approximately 0.3267 $/kg. The cyclic experiments demonstrated the stability of MC-EDM for high-value NaHCO3 recovery. Thus, the MC-EDM pathways contribute significantly to reducing greenhouse gas emissions from industrial processes while promoting resource efficiency and economic sustainability.

A highly-selective biomimetic potassium channel.

Reproducing the outstanding selectivity achieved by biological ion channels in artificial channel systems can revolutionize applications ranging from membrane filtration to single-molecule sensing technologies, but achieving this goal remains a challenge. Herein, inspired by the selectivity filter structure of the KcsA potassium channel, we propose a design of biomimetic potassium nanochannels by functionalizing the wall of carbon nanotubes with an array of arranged carbonyl oxygen atoms. Our extensive molecular dynamics simulations show that the biomimetic nanochannel exhibits a high K+ permeation rate along with a high K+/Na+ selectivity ratio. The free energy calculations suggest that the low Na+ permeability is the result of the higher energy barrier for Na+ than K+ at the channel entrance and ion binding sites. In addition, reducing the number of ion binding sites leads to an increase in the permeation rate but a decrease in selectivity. These findings not only hold promise for the design of high-performance membranes but also help understand the mechanism of selective ion transport in biological ion channels.

Advanced Development of Molecularly Imprinted Membranes for Selective Separation.

Molecularly imprinted membranes (MIMs), the incorporation of a given target molecule into a membrane, are generally used for separating and purifying the effective constituents of various natural products. They have been in use since 1990. The application of MIMs has been studied in many fields, including separation, medicine analysis, solid-phase extraction, and so on, and selective separation is still an active area of research. In MIM separation, two important membrane performances, flux and permselectivities, show a trade-off relationship. The enhancement not only of permselectivity, but also of flux poses a challenging task for membranologists. The present review first describes the recent development of MIMs, as well as various preparation methods, showing the features and applications of MIMs prepared with these different methods. Next, the review focuses on the relationship between flux and permselectivities, providing a detailed analysis of the selective transport mechanisms. According to the majority of the studies in the field, the paramount factors for resolving the trade-off relationship between the permselectivity and the flux in MIMs are the presence of effective high-density recognition sites and a high degree of matching between these sites and the imprinted cavity. Beyond the recognition sites, the membrane structure and pore-size distribution in the final imprinted membrane collectively determine the selective transport mechanism of MIM. Furthermore, it also pointed out that the important parameters of regeneration and antifouling performance have an essential role in MIMs for practical applications. This review subsequently highlights the emerging forms of MIM, including molecularly imprinted nanofiber membranes, new phase-inversion MIMs, and metal-organic-framework-material-based MIMs, as well as the construction of high-density recognition sites for further enhancing the permselectivity/flux. Finally, a discussion of the future of MIMs regarding breakthroughs in solving the flux-permselectivity trade-off is offered. It is believed that there will be greater advancements regarding selective separation using MIMs in the future.

Mechanistic investigation of intensified separation of molybdenum(VI) and vanadium(V) using polymer inclusion membrane electrodialysis

The main challenge in separating molybdenum(VI) and vanadium(V) which have similar properties results in great difficulties in the green recycling of hazardous spent catalysts. Here, selective facilitating transport and stripping are integrated into the polymer inclusion membrane electrodialysis process (PIMED) to separate Mo(VI) and V(V) to overcome the complicated co-extraction and stepwise-stripping in conventional solvent extraction. The influences of various parameters, the selective transport mechanism, and respective activation parameters were systematically investigated. Results revealed that the affinity of the Aliquat 36 as the carrier and PVDF-HFP as the base polymer of PIM towards Mo(VI) is stronger than that of V(V), while the strong interaction between Mo(VI) and carrier caused low migration through the membrane. By the combination of adjusting and controlling the electric density and strip acidity, the interaction was destroyed and the transport was facilitated. After optimization, stripping efficiencies of Mo(VI) and V (V) increased from 44.4% to 93.1% and reduced from 31.9% to 1.8%, respectively, while their separation coefficient increased 16.3 times to 333.4. The activation energy, enthalpy and entropy for the transport of Mo(VI) were determined to be 4.846 kJ mol−1, 6.745 kJ mol−1 and − 310.838 J mol−1 K−1, respectively. The present work demonstrates that the separation of similar metal ions could be improved by fine tuning the affinity and interaction between metal ions and the PIM, thus providing new insights into the recycling of similar metal ions from secondary resources.

Bioinspired Solid‐State Ion Nanochannels: Insight from Channel Fabrication and Ion Transport

AbstractWith specific structures and unique features, biological ion channel proteins play crucial roles in many life processes of living organisms. Inspired by the biological ion channel proteins, researchers have developed a variety of artificial nanochannels to explore the mechanisms of selective ion transport and achieve applications in molecular filters, biosensors, and energy conversion devices. The ion transport behavior in nanochannels is mainly governed by the interaction between ions and the nanochannels interface. Herein, the structures, fabrication methods, and ion transport properties of biomimetic solid‐state ion nanochannels are reviewed, with emphasis on the transport performance and mechanism of nanochannels. In addition, the current challenges faced and the future outlooks of these solid‐sate ion nanochannels for practical applications are discussed.

Transport of heterometric sediments in wave-dominated flows – Tracer experiments

Sediment dynamics is a complex subject, playing an important role in coastal areas. The interaction between wave action and sediment particles is determinant to understand sediment transport processes. The knowledge of sediment transport comprising sand mixtures is relevant as coastal areas, usually, present heterogeneities of sediment particle sizes in the horizontal and vertical directions, denoting the existence of selective transport processes. This study investigates the effects of non-cohesive size-graded sands on sediment transport fluxes to understand selective transport mechanisms under wave-dominated conditions. A laboratory experiment was carried out at the large wave flume (Großer Wellenkanal, GWK) in Hannover, considering distinct sediment mixtures between two well-sorted sands with median grain sizes of 0.21 mm and 0.58 mm. The experiments were carried out for four sediment bed configurations with two different wave energy conditions. A fluorescent sand tracer technique was implemented to measure total and fractional net sediment transport rates and the outcomes are compared with the ones obtained with the mass conservation method. The experimental results show the occurrence of the interaction between different sand fractions: a decrease in the transport of fine sediments and an enhancement of the transport of the coarse sediments as the percentage of coarse sediments in the bed mixture increases. These effects are larger as the coarser fraction in the sand bed increases and they are noticeable for different sediment transport regimes (sheet flow and rippled beds).

Roles of Anion–Cation Coupling Transport and Dehydration-Induced Ion–Membrane Interaction in Precise Separation of Ions by Nanofiltration Membranes

Nanofiltration (NF) membranes are playing increasingly crucial roles in addressing emerging environmental challenges by precise separation, yet understanding of the selective transport mechanism is still limited. In this work, the underlying mechanisms governing precise selectivity of the polyamide NF membrane were elucidated using a series of monovalent cations with minor hydrated radius difference. The observed selectivity of a single cation was neither correlated with the hydrated radius nor hydration energy, which could not be explained by the widely accepted NF model or ion dehydration theory. Herein, we employed an Arrhenius approach combined with Monte Carlo simulation to unravel that the transmembrane process of the cation would be dominated by its pairing anion, if the anion has a greater transmembrane energy barrier, due to the constraint of anion-cation coupling transport. Molecular dynamics simulations further revealed that the distinct hydration structure was the primary origin of the energy barrier difference of cations. The cation having a larger incompressible structure after partial dehydration through subnanopores would induce a more significant ion-membrane interaction and consequently a higher energy barrier. Moreover, to validate our proposed mechanisms, a membrane grafting modification toward enlarging the energy barrier difference of dominant ions achieved a 3-fold enhancement in ion separation efficiency. Our work provides insights into the precise separation of ionic species by NF membranes.

Bridging Database and Experimental Analysis to Reveal Super-hydrodynamic Conductivity Scaling Regimes in Ionic Liquids.

Ion transport through electrolytes critically impacts the performance of batteries and other devices. Many frameworks used to model ion transport assume hydrodynamic mechanisms and focus on maximizing conductivity by minimizing viscosity. However, solid-state electrolytes illustrate that non-hydrodynamic ion transport can define device performance. Increasingly, selective transport mechanisms, such as hopping, are proposed for concentrated electrolytes. However, viscosity-conductivity scaling relationships in ionic liquids are often analyzed with hydrodynamic models. We report data-centric analyses of hydrodynamic transport models of viscosity-conductivity scaling in ionic liquids by merging three databases to bridge physical properties and computational descriptors. With this expansive database, we constrained scaling analyses using ion sizes defined from simulated volumes, as opposed to estimating sizes from activity coefficients. Remarkably, we find that many ionic liquids exhibit positive deviations from the Nernst-Einstein model, implying ions move faster than hydrodynamics should allow. We verify these findings using microrheology and conductivity experiments. We further show that machine learning tools can improve predictions of conductivity from molecular properties, including predictions from solely computational features. Our findings reveal that many ionic liquids exhibit super-hydrodynamic viscosity-conductivity scaling, suggesting mechanisms of correlated ion motion, which could be harnessed to enhance electrochemical device performance.

Supramolecular Mechanosensitive Potassium Channel Formed by Fluorinated Amphiphilic Cyclophane.

Inspired by mechanosensitive potassium channels found in nature, we developed a fluorinated amphiphilic cyclophane composed of fluorinated rigid aromatic units connected via flexible hydrophilic octa(ethylene glycol) chains. Microscopic and emission spectroscopic studies revealed that the cyclophane could be incorporated into the hydrophobic layer of the lipid bilayer membranes and self-assembled to form a supramolecular transmembrane ion channel. Current recording measurements using cyclophane-containing planer lipid bilayer membranes successfully demonstrated an efficient transmembrane ion transport. We also demonstrated that the ion transport property was sensitive to the mechanical forces applied to the membranes. In addition, ion transport assays using pH-sensitive fluorescence dye revealed that the supramolecular channel possesses potassium ion selectivity. We also performed all-atom hybrid quantum-mechanical/molecular mechanical simulations to assess the channel structures at atomic resolution and the mechanism of selective potassium ion transport. This research demonstrated the first example of a synthetic mechanosensitive potassium channel, which would open a new door to sensing and manipulating biologically important processes and purification of key materials in industries.

Selective Transport in the Nuclear Pore Complex

Nuclear pore complexes (NPCs) mediate nucleocytoplasmic exchange controlling the flow of molecules into and out of the nucleus. The selective filter properties of NPCs enable translocation of specific molecules known as nuclear transport factors (NTRs) and their cargo. Central to this selectivity barrier is a group of largely intrinsically disordered nucleoporins (Nups) that contain multiple phenylalanine‐glycine repeats, termed FG Nups. The interactions between FG Nups and NTRs enable NTRs to translocate rapidly yet selectively through the NPC in what is referred to as the “transport paradox”. FG Nups in the NPC have a small folded anchor region tethering them to the NPC outer ring and otherwise are fully disordered, random coil polymers that remain predominantly disordered while engaged to NTRs. FG Nups interact with NTRs using mainly their FG motifs and minimally their intervening spacer residues. The overall enthalpy of the interaction increases as multivalency increases the frequency of individually weak FG‐NTR contacts. Tight binding is limited by an entropy penalty that disfavors simultaneous engagements of FG motifs. Small angle neutron scattering (SANS) shows that the entropy loss is partly due to the local rigidity of an FG motif in the interacting state(Fig 1). All‐atom molecular dynamics (MD) simulation indicates that spacers between the FG motifs behave as “entropic springs”, disfavoring any static binding of the FG repeats. The dynamics of FG Nups enables the FG motifs to slide along the hydrophobic patches of NTRs enabling FG motifs to be easily displaced by other competing FG motifs (Fig. 2). This explanation provides a simple hypothesis for the rapid exchange of FG motif contacts during transport, focusing on the entropic exclusion of non‐NTRs, and ‘solubilization’ of NTR complexes, in contrast to possible condensate formation which would provide a compartmentalization of components. These results reveal fundamental aspects of the functioning mechanisms underlying NPC transport at high structural resolution, something lacking in current models of nuclear transport.1. Sparks, S., et al., Analysis of Multivalent IDP Interactions: Stoichiometry, Affinity, and Local Concentration Effect Measurements. Methods Mol Biol, 2020. 2141: p. 463‐475.2. Sparks, S., et al., Deciphering the “Fuzzy” Interaction of FG Nucleoporins and Transport Factors Using Small‐Angle Neutron Scattering. Structure, 2018. 26(3): p. 477‐484 e4.3. Hayama, R., et al., Thermodynamic characterization of the multivalent interactions underlying rapid and selective translocation through the nuclear pore complex. J Biol Chem, 2018. 293(12): p. 4555‐4563.4. Hough, L.E., et al., The molecular mechanism of nuclear transport revealed by atomic‐scale measurements. Elife, 2015. 4.5. Raveh, B., et al., Slide‐and‐exchange mechanism for rapid and selective transport through the nuclear pore complex. Proc Natl Acad Sci U S A, 2016. 113(18): p. E2489‐97.

Mechanistic insights into the selective mass-transport and fabrication of holey graphene-based membranes for water purification applications

• Critical review on holey graphene (HG)-based membrane for water purification. • HG membranes have high efficiency, selectivity, and superior water permeability. • Mechanistic insights into the mass-transport of HG-based membranes are discussed. • An overview on the fabrication methodologies of HG-based membranes is highlighted. • The performance development of HG-based membranes and challenges are detailed. Graphene (Gr) and its derivative nanomaterials enable a novel approach to manipulate selective mass transport mechanisms at the sub-nanoscale level. These nanomaterials can maintain d-spacing at the sub-nanoscale level amidst their rigid nanosheet frame structure. Unlike other nanomaterials, they have outstanding features such as atomic thickness, extraordinary mechanical strength, and superior chemical stability. Although they could be utilized to overcome crucial challenges in various water purification applications, they usually suffer from swelling and limited penetration. Holey graphene (HG; also known as nanoporous graphene or graphene nano-mesh) is an exceptional derivative of Gr created by eliminating some atoms from the graphite structure to create distributed pores in the atomic structure of Gr nanosheets. These pores, occasionally with ample reactive functional groups near their boundaries, resulted in favorable defects features, which influence the intact Gr nanosheets structure, however they are beneficial in different water purification and desalination applications. In this review, the different approaches for fabricating HG-based membranes along with mass-transport mechanisms including experimental and simulation outcomes are presented and discussed. Related applications that exploit the extraordinary structure of the HG nanomaterial are also reviewed.

Instruction Tools for Signal Processing and Machine Learning for Ion-Channel Sensors

Ion Channel sensors have several applications including DNA sequencing, biothreat detection, and medical applications. Ion-channel sensors mimic the selective transport mechanism of cell membranes and can detect a wide range of analytes at the molecule level. Analytes are sensed through changes in signal patterns. Papers in the literature have described different methods for ion channel signal analysis. In this paper, we describe a series of new graphical tools for ion channel signal analysis which can be used for research and education. The paper focuses on the utility of this tools in biosensor classes. Teaching signal processing and machine learning for ion channel sensors is challenging because of the multidisciplinary content and student backgrounds which include physics, chemistry, biology and engineering. The paper describes graphical ion channel analysis tools developed for an on-line simulation environment called J-DSP. The tools are integrated and assessed in a graduate bio-sensor course through computer laboratory exercises.

High Osmotic Power Generation via Nanopore Arrays in Hybrid Hexagonal Boron Nitride/Silicon Nitride Membranes.

Nanopores embedded in two-dimensional (2D) nanomaterials are a promising emerging technology for osmotic power generation. Here, coupling our new AFM-based pore fabrication approach, tip-controlled local breakdown (TCLB), with a hybrid membrane formed by coating silicon nitride (SiN) with hexagonal boron nitride (hBN), we show that high osmotic power density can be obtained in systems that do not possess the thinness of atomic monolayers. In our approach, the high osmotic performance arises from charge separation induced by the highly charged hBN surface rather than charge on the inner pore wall. Moreover, exploiting TCLB's capability of producing sub 10 nm pore arrays, we investigate the effects of pore-pore interaction on the overall power density. We find that an optimum pore-to-pore spacing of ∼500 nm is required to maintain an efficient selective transport mechanism.

Carotenoid profile in breast milk and maternal and cord plasma: a longitudinal study in Southwest China.

Carotenoids are increasingly being implicated to have an important role in brain and eye development. This study aimed to quantify the content and profile of carotenoids in human breast milk, maternal plasma and neonatal umbilical cord plasma in Chengdu, an urban area in Southwest China. In this study, fifty-four healthy mothers were enrolled. Maternal blood, umbilical cord blood, colostrum, transitional milk and mature milk were collected. Concentrations of carotenoids (lutein, zeaxanthin, β-cryptoxanthin, β-carotene and lycopene) were analysed by HPLC. We found that carotenoid concentrations decreased from colostrum to mature milk. Hydrocarbon carotenoids with weaker polarity decreased more than the polar carotenoids. Lycopene concentrations dropped by 99 %, β-carotene by 92 %, β-cryptoxanthin by 83 %, lutein by 32 % and zeaxanthin by 22 %. Lycopene and β-carotene accounted for 70 % of the total carotenoids in colostrum, and lutein predominated amongst carotenoids in transitional milk and mature milk (51-55 %). Carotenoid concentrations in maternal plasma were much higher than that in cord plasma. Lutein predominated in cord plasma. The concentrations of all carotenoids in maternal plasma were correlated with those of cord plasma and human milk. These results are consistent with selective transport mechanisms in the mammary gland related to the polarity of carotenoids, and each carotenoid has its own implications, which may have different priorities in the early life development of infants. These findings may help guide dietary recommendations for carotenoid inclusion in infant formulas.

Artificial Water Channels: Towards Biomimetic Membranes for Desalination.

Natural Aquaporin (AQP) channels are efficient water translocating proteins, rejecting ions. Inspired by this masterpiece of nature, Artificial Water Channels (AWCs) with controlled functional structures, can be potentially used to mimic the AQPs to a certain extent, offering flexible avenues toward biomimetic membranes for water purification. The objective of this paper is to trace the historical development and significant advancements of current reported AWCs. Meanwhile, we attempt to reveal important structural insights and supramolecular self-assembly principles governing the selective water transport mechanisms, toward innovative AWC-based biomimetic membranes for desalination.

Design and fabrication of highly selective and permeable polymer membranes

Selective polymer membranes are one of the most promising materials to achieve large-scale and energy-efficient mass separation and energy conversion. However, their performance is subject to the selectivity–permeability trade-off. To overcome this trade-off and achieve high-performance ion separation, it is essential to fabricate thin membranes with a high density of uniformly sized nanopores with the pore size at around 1 nm. However, it has been challenging to precisely control the pore size at about 1 nm. In this Tutorial, we outline the underlying mechanism for selective ion transport through nanopores, especially the emerging mechanism as the nanopore size is tuned around 1 nm. Then, we review the recent development of the main fabrication methods of selective polymer membranes from either the top–down approach or the bottom–up approach, especially the novel techniques generating uniformly sized nanopores with nanometric or even subnanometric size. Finally, we discuss the future development of the design and fabrication of the selective polymer membranes to fulfill their potential in real applications.

Cryo-EM structure of the human concentrative nucleoside transporter CNT3.

Concentrative nucleoside transporters (CNTs), members of the solute carrier (SLC) 28 transporter family, facilitate the salvage of nucleosides and therapeutic nucleoside derivatives across the plasma membrane. Despite decades of investigation, the structures of human CNTs remain unknown. We determined the cryogenic electron microscopy (cryo-EM) structure of human CNT (hCNT) 3 at an overall resolution of 3.6 Å. As with its bacterial homologs, hCNT3 presents a trimeric architecture with additional N-terminal transmembrane helices to stabilize the conserved central domains. The conserved binding sites for the substrate and sodium ions unravel the selective nucleoside transport and distinct coupling mechanism. Structural comparison of hCNT3 with bacterial homologs indicates that hCNT3 is stabilized in an inward-facing conformation. This study provides the molecular determinants for the transport mechanism of hCNTs and potentially facilitates the design of nucleoside drugs.

A Method to Quantify Molecular Diffusion within Thin Solvated Polymer Films: A Case Study on Films of Natively Unfolded Nucleoporins

We present a method to probe molecular and nanoparticle diffusion within thin, solvated polymer coatings. The device exploits the confinement with well-defined geometry that forms at the interface between a planar and a hemispherical surface (of which at least one is coated with polymers) in close contact and uses this confinement to analyze diffusion processes without interference of exchange with and diffusion in the bulk solution. With this method, which we call plane–sphere confinement microscopy (PSCM), information regarding the partitioning of molecules between the polymer coating and the bulk liquid is also obtained. Thanks to the shape of the confined geometry, diffusion and partitioning can be mapped as a function of compression and concentration of the coating in a single experiment. The method is versatile and can be integrated with conventional optical microscopes; thus it should find widespread use in the many application areas exploiting functional polymer coatings. We demonstrate the use of PSCM using brushes of natively unfolded nucleoporin domains rich in phenylalanine–glycine repeats (FG domains). A meshwork of FG domains is known to be responsible for the selective transport of nuclear transport receptors (NTRs) and their macromolecular cargos across the nuclear envelope that separates the cytosol and the nucleus of living cells. We find that the selectivity of NTR uptake by FG domain films depends sensitively on FG domain concentration and that the interaction of NTRs with FG domains obstructs NTR movement only moderately. These observations contribute important information to better understand the mechanisms of selective NTR transport.

A two-lane mechanism for selective biological ammonium transport.

The transport of charged molecules across biological membranes faces the dual problem of accommodating charges in a highly hydrophobic environment while maintaining selective substrate translocation. This has been the subject of a particular controversy for the exchange of ammonium across cellular membranes, an essential process in all domains of life. Ammonium transport is mediated by the ubiquitous Amt/Mep/Rh transporters that includes the human Rhesus factors. Here, using a combination of electrophysiology, yeast functional complementation and extended molecular dynamics simulations, we reveal a unique two-lane pathway for electrogenic NH4+ transport in two archetypal members of the family, the transporters AmtB from Escherichia coli and Rh50 from Nitrosomonas europaea. The pathway underpins a mechanism by which charged H+ and neutral NH3 are carried separately across the membrane after NH4+ deprotonation. This mechanism defines a new principle of achieving transport selectivity against competing ions in a biological transport process.

A two-lane mechanism for selective biological ammonium transport

The transport of charged molecules across biological membranes faces the dual problem of accommodating charges in a highly hydrophobic environment while maintaining selective substrate translocation. A particular controversy has existed around the mechanism of ammonium exchange by the ubiquitous Amt/Mep/Rh transporter family, an essential process in all kingdoms of life. Here, using a combination of SSME electrophysiology, yeast functional complementation, and extended molecular dynamics simulations, we reveal a unique two-lane pathway for electrogenic NH4+transport in two archetypal members of the family. The pathway underpins a mechanism by which charged H+and neutral NH3 are carried separately across the membrane after NH4+deprotonation. This mechanism defines a new principle of achieving transport selectivity against competing ions in a biological transport process.