Membranes, Volume 13, Issue 8 (August 2023) – 58 articles

Ultrafiltration (UF) polymeric membranes are widely used in water treatment and support desalination and gas separation membranes. In this article, we enhance the performance of Polysulfone (PSF) mixed matrix membranes (MMMs) by dispersing different concentrations of thermally reduced graphene (TRG) nanofillers. The UF PSF-TRG MMMs were fabricated via the phase inversion process, and the impact of TRG loading on the characteristics of the membrane, including hydrophilicity, porosity, roughness, and morphology, were analyzed using a contact angle measurement, atomic force microscopy (AFM), scanning electron microscopy (SEM), and dynamic mechanical analysis. Incorporating TRG into the PSF matrix led to favorable effects in the instantaneous de-mixing during phase inversion, increasing the porosity and hydrophilicity of MMMs and improving the mechanical properties of the membranes. Moreover, membrane performance was examined to remove dispersed oil from oil–water emulsion and support air-dehumidification membranes. MMM performance in terms of flux and oil rejection was superior to the control PSF membrane. Incorporating 0.25% TRG into PSF resulted in a 70% water flux increase and higher oil rejection compared to the control PSF membrane. As a support for air-dehumidification membranes, the MMM also demonstrated enhanced humidity reduction and an over 20% increase in water vapor permeance over the control PSF membrane. These results indicate that the PSF-TRG MMMs are an excellent candidate for reliable oil–water separation and as a support for air-dehumidification membranes. Full article

Modernization of wastewater treatment plants is usually caused by their significant wear and changes in the flow rate and concentration of pollutants. If there is no initial data on the flow or pollution, their determination by calculation is required, which may lead to an increase in concentration. Within the study, the modernization of treatment facilities was estimated under conditions of reduced flow and increased pollution concentration. Calculations were carried out both manually and using the CapdetWorks software package. The focus was on secondary treatment facilities as the main element of the municipal wastewater treatment plant within their upgrade from only organic pollutants removal (plug–flow reactor) to removal of both organic pollutants and nutrients (technology of the University of Cape Town). The calculations of tank volumes have shown that the concentration of pollutants has a much greater impact on them than the change in flow, especially when improvement in the treatment quality is required. The study revealed that membrane sludge separation allows tanks to be reduced in volume by 1.5–2.5 times (depending on the value of mixed liquor suspended solids) in comparison with gravity separation, which means smaller capital costs. However, membrane application requires significant energy costs for membrane aeration. For the initial data of the study, the specific energy costs for aeration before the upgrade, after the upgrade (gravity separation), and after the upgrade (membrane separation) were 0.12 kWh/m³, 0.235 kWh/m³, and 0.3 kWh/m³, respectively. If the membrane lifetime is 10 years, membrane costs were determined to be 10–15% of the energy costs for aeration. Full article

Currently, understanding the dynamics of the interaction between the agents in a process is one of the most important factors regarding its operation and design. Membrane processes for industrial wastewater management are not strangers to this topic. One such example is the concentration of compounds with high added value, such as the phenolic compounds present in olive mill wastewater (OMW). This process is a viable option, thanks to the forward osmosis (FO) process, osmotically driven by a saline stream. In this context, the transport of the solute and the solvent through the FO membranes, although essential to the process, remains problematic. This paper presents a study to predict, by means of a theoretical model, the water flux for two membranes (a cellulose triacetate flat sheet and a polyamide hollow fiber with integrated aquaporin proteins) with different characteristics using a sodium chloride solution as the draw solution (DS). The novelty of this model is the consideration of the contribution of organic compounds (in addition to the inorganic salts) to the osmotic pressure in the feed side. Moreover, the geometry of the modules and the characteristics of the membranes were also considered. The model was developed with the ability to run under different conditions, with or without tyrosol (the compound chosen as representative of OMW phenolic compounds) in the feed solution (FS), and was fitted and evaluated using experimental data. The results presented a variability in the model prediction, which was a function of both the membrane used and the FS and DS, with a greater influence of tyrosol observed on the permeate flux in the flat cellulose triacetate membrane. Full article

In this study, polyethersulfone (PES) ultrafiltration (UF) membranes were modified with GO, Ag, ZnO, Ag-GO and ZnO-GO nanoparticles to improve carbamazepine removal and fouling prevention by making membrane surfaces more hydrophilic. The fabricated membranes were characterized for surface and cross-sectional morphology, surface roughness and zeta potential, as well as hydrophilicity, functional groups, surface tension parameters and water permeability Thereafter, the membranes were evaluated for their efficiency in removing MgSO₄ and carbamazepine as well as antifouling properties. To understand the role of affinity interactions in rejection and fouling, membrane–solute adhesion energies (${∆G}_{slm}$) were quantified based on the Lifshitz–van der Waals/acid–base method. Unlike previous studies, which have generalized fouling prevention to be due to improvements in hydrophilicity upon adding nanoparticles, this work further explored the role of surface tension components on rejection and fouling prevention. The addition of nanoparticles improved membrane hydrophilicity (77–62°), water permeability (11.9–17.7 Lm⁻² h⁻¹ bar⁻¹), mechanical strength (3.46–4.11 N/mm²), carbamazepine rejection (30–85%) and fouling prevention (60–23% flux decline). Rejection and antifouling properties increased as ${∆G}_{slm}$ became more repulsive (i.e., less negative). Membrane modification reduced irreversible fouling, and the fouled membranes were cleaned by flushing with water. Fouling related more to membrane electron donor components (${\gamma }^{-}$), while the roles of electron acceptor (${\gamma }^{+}$) and Lifshitz–van der Waals components (${\gamma }^{LW}$) were less important. This work provides more insights into the role of affinity interactions in rejection and fouling and how rejection and fouling mechanisms change with nanoparticle addition. Full article

The present work investigates nanofiltration (NF) and ultrafiltration (UF) for the removal of three widely used pharmaceutically active compounds (PhACs), namely atenolol, sulfamethoxazole, and rosuvastatin. Four membranes, two polyamide NF membranes (NF90 and NF270) and two polyethersulfone UF membranes (XT and ST), were evaluated in terms of productivity (permeate flux) and selectivity (rejection of PhACs) at pressures from 2 to 8 bar. Although the UF membranes have a much higher molecular weight cut-off (1000 and 10,000 Da), when compared to the molecular weight of the PhACs (253–482 Da), moderate rejections were observed. For UF, rejections were dependent on the molecular weight and charge of the PhACs, membrane molecular weight cut-off (MWCO), and operating pressure, demonstrating that electrostatic interactions play an important role in the removal of PhACs, especially at low operating pressures. On the other hand, both NF membranes displayed high rejections for all PhACs studied (75–98%). Hence, considering the optimal operating conditions, the NF270 membrane (MWCO = 400 Da) presented the best performance, achieving permeate fluxes of about 100 kg h⁻¹ m⁻² and rejections above 80% at a pressure of 8 bar, that is, a productivity of about twice that of the NF90 membrane (MWCO = 200 Da). Therefore, NF270 was the most suitable membrane for this application, although the tight UF membranes under low operating pressures displayed satisfactory results. Full article

An experimental laboratory set of samples of composite heterogeneous anion-exchange membranes was obtained by us for the development of our original method of polycondensation filling. Anion-exchange membranes were prepared on plasma-treated and non-plasma-treated polyester fiber fabrics. The fabric was treated with low-temperature argon plasma at a power of 400 W for 10 min at a pressure of 5 × 10⁻⁵ mbar. On the surface and bulk of the polyester fiber, a polyfunctional anionite of mixed basicity was synthesized and formed. The anion-exchange membrane contained secondary and tertiary amino groups and quaternary ammonium groups, which were obtained from polyethylene polyamines and epichlorohydrins. At the stage of the chemical synthesis of the anion matrix, oxidized nanoparticles (~1.5 wt.%) of silicon, nickel, and iron were added to the monomerization composition. The use of ion-plasma processing of fibers in combination with the introduction of oxidized nanoparticles at the synthesis stage makes it possible to influence the speed and depth of the synthesis and curing processes; this changes the formation of the surface morphology and the internal structure of the ion-exchange polymer matrix, as well as the hydrophobic/hydrophilic balance and—as a result—the different operational characteristics of anion-exchange membranes. Full article

In a single-step spinning process, we create a thin-walled, robust hollow fiber support made of Torlon^® polyamide-imide featuring an intermediate polyethyleneimine (PEI) lumen layer to facilitate the integration and covalent attachment of a dense selective layer. Subsequently, interfacial polymerization of m-phenylenediamine and trimesoyl chloride forms a dense selective polyamide (PA) layer on the inside of the hollow fiber. The resulting thin-film composite hollow fiber membranes show high NaCl rejections of around 96% with a pure water permeability of $1.2$ LMH/bar. The high success rate of fabricating the thin-film composite hollow fiber membrane proves our hypothesis of a supporting effect of the intermediate PEI layer on separation layer formation. This work marks a step towards the development of a robust method for the large-scale manufacturing of thin-film composite hollow fiber membranes for reverse osmosis and nanofiltration. Full article

A partial least squares (PLS) quantitative chemometric method based on the analysis of the mid-Fourier transform infrared spectroscopy (MID-FTIR) spectrum of polymer inclusion membranes (PIMs) used for the extraction of Cr(VI) from aqueous media is developed. The system previously optimized considering the variables membrane composition, extraction time, and pH, is characterized in terms of its adsorption isotherm, distribution coefficient, extraction percent, and enrichment factor. A Langmuir-type adsorption behavior with K_L = 2199 cm³/mmol, q_max = 0.188 mmol/g, and 0 < R_L < 1 indicates that metal adsorption is favorable. The characterization of the extraction reaction is performed as well, showing a 1:1 Cr(VI):Aliquat 336 ratio, in agreement with solvent extraction data. The principal component analysis (PCA) of the PIMs reveals a complex pattern, which is satisfactorily simplified and related to Cr(VI) concentrations through the use of a variable selection method (iPLS) in which the bands in the ranges 3451–3500 cm⁻¹ and 3751–3800 cm⁻¹ are chosen. The final PLS model, including the 100 wavelengths selected by iPLS and 10 latent variables, shows excellent parameter values with root mean square error of calibration (RMSEC) of 3.73115, root mean square error of cross-validation (RMSECV) of 6.82685, bias of −1.91847 × 10⁻¹³, cross-validation (CV) bias of 0.185947, R² Cal of 0.98145, R² CV of 0.940902, recovery% of 104.02 ± 4.12 (α = 0.05), sensitivity% of 0.001547 ppb, analytical sensitivity (γ) of 3.8 ppb, γ⁻¹: 0.6 ppb⁻¹, selectivity of 0.0155, linear range of 5.8–100 ppb, limit of detection (LD) of 1.9 ppb, and limit of quantitation (LQ) of 5.8 ppb. The developed PIM sensor is easy to implement as it requires few manipulations and a reduced number of chemical compounds in comparison to other similar reported systems. Full article

Electrochemical characterization of positively and negatively charged membranes is performed by analyzing membrane potential values on the basis of the Teorell–Meyer–Sievers (TMS) model. This analysis allows the separate estimation of Donnan (interfacial effects) and diffusion (differences in ions transport through the membrane) contributions, and it permits the evaluation of the membrane’s effective fixed charge concentration and the transport number of the ions in the membrane. Typical ion-exchange commercial membranes (AMX, Ionics or Nafion) are analyzed, though other experimental and commercial membranes, which are derived from different materials and have diverse structures (dense, swollen or nanoporous structures), are also considered. Moreover, for some membranes, changes associated with different modifications and other effects (concentration gradient or level, solution stirring, etc.) are also analyzed. Full article

Catalyst recovery is a major challenge for reaching the objectives of green chemistry for industry. Indeed, catalysts enable quick and selective syntheses with high reaction yields. This is especially the case for homogeneous platinoid catalysts which are almost indispensable for cross-coupling reactions often used by the pharmaceutical industry. However, they are based on scarce, expensive, and toxic resources. In addition, they are quite sensitive and degrade over time at the end of the reaction. Once degraded, their regeneration is complex and hazardous to implement. Working on their recovery could lead to highly effective catalytic chemistries while limiting the environmental and economic impacts of their one-time uses. This review aims to describe and compare conventional processes for metal removal while discussing their advantages and drawbacks considering the objective of homogeneous catalyst recovery. Most of them lead to difficulty recycling active catalysts due to their ability to only treat metal ions or to chelate catalysts without the possibility to reverse the mechanism. However, membrane processes seem to offer some perspectives with limiting degradations. While membranes are not systematically the best option for recycling homogeneous catalysts, current development might help improve the separation between pharmaceutical active ingredients and catalysts and enable their recycling. Full article

PSD95-disc large-zonula occludens (PDZ) domains are globular modules of 80–90 amino acids that co-evolved with multicellularity. They commonly bind to carboxy-terminal sequences of a plethora of membrane-associated proteins and influence their trafficking and signaling. We previously built a PDZ resource (PDZome) allowing us to unveil human PDZ interactions by Yeast two-hybrid. Yet, this resource is incomplete according to the current knowledge on the human PDZ proteome. Here we built the PDZome 2.0 library for Yeast two-hybrid, based on a PDZ library manually curated from online resources. The PDZome2.0 contains 305 individual clones (266 PDZ domains in isolation and 39 tandems), for which all boundaries were designed based on available PDZ structures. Using as bait the E6 oncoprotein from HPV16, a known promiscuous PDZ interactor, we show that PDZome 2.0 outperforms the previous resource. Full article

Membrane biofouling is the consequence of the deposition of microorganisms on polymer membrane surfaces. Polymeric membranes have garnered more attention for filtering and purifying water because of their ease of handling, low cost, effortless surface modification, and mechanical, chemical, and thermal properties. The sizes of the pores in the membranes enable micro- and nanofiltration, ultrafiltration, and reverse osmosis. Commonly used polymers for water filter membranes are polyvinyl chloride (PVA), polyvinylidene fluoride (PVDF), polyamide (PA), polyethylene glycol (PEG), polyethersulfone (PES), polyimide (PI), polyacrylonitrile (PAN), polyvinyl alcohol (PA), poly (methacrylic acid) (PMAA), polyaniline nanoparticles (PANI), poly (arylene ether ketone) (PAEK), polyvinylidene fluoride polysulfone (PSF), poly (ether imide) (PEI), etc. However, these polymer membranes are often susceptible to biofouling because of inorganic, organic, and microbial fouling, which deteriorates the membranes and minimizes their lives, and increases operating costs. Biofouling infection on polymer membranes is responsible for many chronic diseases in humans. This contamination cannot be eliminated by periodic pre- or post-treatment processes using biocides and other chemicals. For this reason, it is imperative to modify polymer membranes by surface treatments to enhance their efficiency and longevity. The main objective of this manuscript is to discuss application-oriented approaches to control biofouling on polymer membranes using various surface treatment methods, including nanomaterials and fouling characterizations utilizing advanced microscopy and spectroscopy techniques. Full article

Blend membranes consisting of two polymer pairs improve gas separation, but compromise mechanical and thermal properties. To address this, incorporating titanium dioxide (TiO₂) nanoparticles has been suggested, to enhance interactions between polymer phases. Therefore, the objective of this study was to investigate the impact of TiO₂ as a filler on the thermal, surface mechanical, as well as gas separation properties of blend membranes. Blend polymeric membranes consisting of polyetherimide (PEI) and polyvinyl acetate (PVAc) with blend ratios of (99:1) and (98:2) were developed via a wet-phase inversion technique. In the latter, TiO₂ was incorporated in ratios of 1 and 2 wt.% while maintaining a blend ratio of (98:2). TGA and DSC analyses were used to examine thermal properties, and nano-indentation tests were carried out to ascertain surface mechanical characteristics. On the other hand, a gas permeation set-up was used to determine gas separation performance. TGA tests showed that blend membranes containing TiO₂ had better thermal characteristics. Indentation tests showed that TiO₂-containing membranes exhibited greater surface hardness compared to other membranes. The results of gas permeation experiments showed that TiO₂-containing membranes had better separation characteristics. PEI–PVAc blend membranes with 2 wt.% TiO₂ as filler displayed superior separation performance for both gas pairs (CO₂/CH₄ and CO₂/N₂). The compatibility between the rubbery and glassy phases of blend membranes was improved as a result of the inclusion of TiO₂, which further benefited their thermal, surface mechanical, and gas separation performances. Full article

A promising approach that uses the sol–gel method to manufacture new breathable active films with self-cleaning and antibacterial surfaces is based on the PET membranes obtained via ion track technology with a pore density of 10^–7 cm⁻² and a pore diameter of about 500 ± 15 nm, coated with a layer of TiO₂ anatase, with a thickness of up to 80 nm. The formation of the photocatalytically active TiO₂ anatase phase was confirmed using Raman analysis. Coating the PET membrane with a layer of TiO₂ increased the hydrophobicity of the system (CA increased from 64.2 to 92.4, and the antibacterial activity was evaluated using Escherichia coli and Staphylococcus aureus bacteria with the logarithmic reduction factors of 3.34 and 4.24, respectively). Full article

An extreme ultraviolet (EUV) pellicle is an ultrathin membrane at a stand-off distance from the reticle surface that protects the EUV mask from contamination during the exposure process. EUV pellicles must exhibit high EUV transmittance, low EUV reflectivity, and superior thermomechanical durability that can withstand the gradually increasing EUV source power. This study proposes an optimal range of optical constants to satisfy the EUV pellicle requirements based on the optical simulation results. Based on this, zirconium disilicide (ZrSi₂), which is expected to satisfy the optical and thermomechanical requirements, was selected as the EUV pellicle candidate material. An EUV pellicle composite comprising a ZrSi₂ thin film deposited via co-sputtering was fabricated, and its thermal, optical, and mechanical properties were evaluated. The emissivity increased with an increase in the thickness of the ZrSi₂ thin film. The measured EUV transmittance (92.7%) and reflectivity (0.033%) of the fabricated pellicle satisfied the EUV pellicle requirements. The ultimate tensile strength of the pellicle was 3.5 GPa. Thus, the applicability of the ZrSi₂ thin film as an EUV pellicle material was verified. Full article

Direct liquid fuel cells (DLFCs) operate directly on liquid fuel instead of hydrogen, as in proton-exchange membrane fuel cells. DLFCs have the advantages of higher energy densities and fewer issues with the transportation and storage of their fuels compared with compressed hydrogen and are adapted to mobile applications. Among DLFCs, the direct borohydride–hydrogen peroxide fuel cell (DBPFC) is one of the most promising liquid fuel cell technologies. DBPFCs are fed sodium borohydride (NaBH₄) as the fuel and hydrogen peroxide (H₂O₂) as the oxidant. Introducing H₂O₂ as the oxidant brings further advantages to DBPFC regarding higher theoretical cell voltage (3.01 V) than typical direct borohydride fuel cells operating on oxygen (1.64 V). The present review examines different membrane types for use in borohydride fuel cells, particularly emphasizing the importance of using bipolar membranes (BPMs). The combination of a cation-exchange membrane (CEM) and anion-exchange membrane (AEM) in the structure of BPMs makes them ideal for DBPFCs. BPMs maintain the required pH gradient between the alkaline NaBH₄ anolyte and the acidic H₂O₂ catholyte, efficiently preventing the crossover of the involved species. This review highlights the vast potential application of BPMs and the need for ongoing research and development in DBPFCs. This will allow for fully realizing the significance of BPMs and their potential application, as there is still not enough published research in the field. Full article

This work is dedicated to the study of the treatment of multi-walled carbon nanotubes (MWCNTs) with dichromic acid. The dichromic acid was formed by dissolving different concentrations of CrO₃ in water. The effect of the concentration of dichromic acid on the change in texture characteristics, elemental composition, defectiveness, graphitization degree, and surface chemistry of MWCNTs was investigated using various analytical techniques, such as transmission electron microscopy, energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). Testing of MWCNTs as electrodes for supercapacitors in 3.5 M H₂SO₄ solution was carried out using cyclic voltammetry. A decrease in the average diameter of CNTs after treatment was found. The EDX and XPS showed that the oxygen content on the surface of MWCNTs increased after treatment with dichromic acid. The formation of Cr₂O₃ after treatment with dichromic acid was detected by XPS. High angle annular dark field scanning transmission electron microscopy was used to confirm the intercalation of the chromium-containing compound between graphene layers of MWCNTs after treatment with dichromic acid. It was found that two different types of MWCNTs showed diverse behavior after treatment. The highest specific capacitance of the MWCNTs after treatment was 141 F g⁻¹ (at 2 mV s⁻¹) compared to 0.3 F g⁻¹ for the untreated sample. Full article

Technological advances in biosensing offer extraordinary opportunities to transfer technologies from a laboratory setting to clinical point-of-care applications. Recent developments in the field have focused on electrochemical and optical biosensing platforms. Unfortunately, these platforms offer relatively poor sensitivity for most of the clinically relevant targets that can be measured on the skin. In addition, the non-specific adsorption of biomolecules (biofouling) has proven to be a limiting factor compromising the longevity and performance of these detection systems. Research from our laboratory seeks to capitalize on analyte selective properties of biomaterials to achieve enhanced analyte adsorption, enrichment, and detection. Our goal is to develop a functional membrane integrated into a microfluidic sampling interface and an electrochemical sensing unit. The membrane was manufactured from a blend of Polycaprolactone (PCL) and Polyethylene oxide (PEO) through a solvent casting evaporation method. A microfluidic flow cell was developed with a micropore array that allows liquid to exit from all pores simultaneously, thereby imitating human perspiration. The electrochemical sensing unit consisted of planar gold electrodes for the monitoring of nonspecific adsorption of proteins utilizing Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The solvent casting evaporation technique proved to be an effective method to produce membranes with the desired physical properties (surface properties and wettability profile) and a highly porous and interconnected structure. Permeability data from the membrane sandwiched in the flow cell showed excellent permeation and media transfer efficiency with uniform pore activation for both active and passive sweat rates. Biofouling experiments exhibited a decrease in the extent of biofouling of electrodes protected with the PCL/PEO membrane, corroborating the capacity of our material to mitigate the effects of biofouling. Full article

Nanofibrous membranes for membrane distillation (MD) have demonstrated promising results in treating various water and wastewater streams. Significant progress has been made in recent decades because of the development of sophisticated membrane materials, such as superhydrophobic, omniphobic and Janus membranes. However, fouling and wetting remain crucial issues for long-term operation. This mini-review summarizes ideas as well as their limitations in understanding the fouling in membrane distillation, comprising organic, inorganic and biofouling. This review also provides progress in developing antifouling nanofibrous membranes for membrane distillation and ongoing modifications on nanofiber membranes for improved membrane distillation performance. Lastly, challenges and future ways to develop antifouling nanofiber membranes for MD application have been systematically elaborated. The present mini-review will interest scientists and engineers searching for the progress in MD development and its solutions to the MD fouling issues. Full article

Competition for the migration of interfering cations limits the scale-up and implementation of the Donnan dialysis process for the recovery of ammonia nitrogen (NH₄⁺-N) from wastewater in practice. Highly efficient selective permeation of NH₄⁺ through a cation exchange membrane (CEM) is expected to be modulated via tuning the surface charge and structure of CEM. In this work, a novel CEM was designed to form a graphene oxide (GO)-polyethyleneimine (PEI) cross-linked layer by introducing self-assembling layers of GO and PEI on the surface of a commercial CEM, which rationally regulates the surface charge and structure of the membrane. The resulting positively charged membrane surface exhibits stronger repulsion for divalent cations compared to monovalent cations according to Coulomb’s law, while, simultaneously, GO forms π–metal cation conjugates between metal cations (e.g., Mg²⁺ and Ca²⁺), thus limiting metal cation transport across the membrane. During the DD process, higher NH₄⁺ concentrations resulted in a longer time to reach Donnan equilibrium and higher NH₄⁺ flux, while increased Mg²⁺ concentrations resulted in lower NH₄⁺ flux (from 0.414 to 0.213 mol·m⁻²·h⁻¹). Using the synergistic effect of electrostatic interaction and non-covalent cross-linking, the designed membrane, referred to as GO-PEI (20) and prepared by a 20 min impregnation in the GO-PEI mixture, exhibited an NH₄⁺ transport rate of 0.429 mol·m⁻²·h⁻¹ and a Mg²⁺ transport rate of 0.003 mol·m⁻²·h⁻¹ in single-salt solution tests and an NH₄⁺/Mg²⁺ selectivity of 15.46, outperforming those of the unmodified and PEI membranes (1.30 and 5.74, respectively). In mixed salt solution tests, the GO-PEI (20) membrane showed a selectivity of 15.46 (~1.36, the unmodified membrane) for NH₄⁺/Mg²⁺ and a good structural stability after 72 h of continuous operation. Therefore, this facile surface charge modulation approach provides a promising avenue for achieving efficient NH₄⁺-selective separation by modified CEMs. Full article

The hydration of ions and charge groups controls electro mass transfer through ion exchange systems. The self-diffusion and local mobility of water molecules as well as lithium cations in poly (4-styrenesulfonic acid) and its lithium, sodium and cesium salts were investigated for the first time using pulsed-field gradient NMR (PFG NMR) and NMR relaxation techniques. The temperature dependences of the water molecule and Li⁺ cation self-diffusion coefficients exhibited increasing self-diffusion activation energy in temperature regions below 0 °C, which is not due to the freezing of parts of the water. The self-diffusion coefficients of water molecules and lithium cations, as measured using PFG NMR, are in good agreement with the self-diffusion coefficients calculated based on Einstein’s equation using correlation times obtained from spin-lattice relaxation data. It was shown that macroscopic water molecules’ and lithium cations’ transfer is controlled by local particles jumping between neighboring sulfonated groups. These results are similar to the behavior of water and cations in sulfonic cation exchanger membranes and resins. It was concluded that polystyrenesulfonic acid is appropriate model of the ionogenic part of membranes based on this polymer. Full article

Manganese is the Earth’s crust’s third most abundant transition metal. Decades of increased mining activities worldwide have inevitably led to the release of large amounts of this metal into the environment, specifically in water resources. Up to a certain level, manganese acts as an essential micronutrient to maintain health and support the growth and development of microorganisms, plants, and animals, while above a specific limit, manganese can cause toxicity in aquatic and terrestrial ecosystems. There are conventional ways to remove manganese from water, such as chemical precipitation, sorption, and biological methods. However, other treatments have yet to be studied much, such as reverse osmosis (RO), which has demonstrated its effectiveness in the removal of heavy metals and could be a suitable alternative for manganese removal if its energy consumption is reduced. This research presents mathematical and statistical modeling of the behavior of a system in laboratory-scale RO. The principal finding was that it is possible to remove Mn using the RO operated with low pressures without decreasing the sustainable removal efficiency. Reducing the operating costs of RO opens the possibility of implementing RO in different contexts where there are problems with water contamination and economic limitations. Full article

The transport of iron(III) from aqueous solutions through pseudo-emulsion-based hollow fiber with strip dispersion (PEHFSD) was investigated using a microporous hydrophobic hollow fiber membrane module. The pseudo-protic ionic liquid RNH₃HSO₄⁻ dissolved in Solvesso 100 was used as the carrier phase. This pseudo-protic ionic liquid was generated by the reaction of the primary amine Primene JMT (RNH₂) with sulphuric acid. The aqueous feed phase (3000 cm³) containing iron(III) was passed through the tube side of the fiber, and the pseudo-emulsion phase of the carrier phase (400 cm³) and sulphuric acid (400 cm³) were circulated through the shell side in counter-current operational mode, using a single hollow fiber module for non-dispersive extraction and stripping. In the operation, the stripping solution (sulphuric acid) was dispersed into the organic membrane phase in a tank with a mixing arrangement (a four-blade impeller stirrer) designed to provide strip dispersion. This dispersed phase was continuously circulated from the tank to the membrane module in order to provide a constant supply of the organic solution to the fiber pores. Different hydrodynamic and chemical parameters, such as feed (75–400 cm³/min) and pseudo-emulsion phases (50–100 cm³/min) flows, sulphuric acid concentration in the feed and stripping phases (0.01–0.5 M and 0.5–3 M, respectively), metal concentration (0.01–1 g/L) in the feed phase, and PPILL concentration (0.027–0.81 M) in the carrier phase, were investigated. From the experimental data, different diffusional parameters were estimated, concluding that the resistance due to the feed phase was not the rate-controlling step of the overall iron(III) transport process. It was possible to concentrate iron(III) in the strip phase using this smart PEHFSD technology. Full article

Lateral transport and release of protons at the water–membrane interface play crucial roles in cell bioenergetics. Therefore, versatile techniques need to be developed for investigating as well as clarifying the main features of these processes at the molecular level. Here, we experimentally measured the kinetics of binding of protons released from the photoactivated compound sodium 2-methoxy-5-nitrophenyl sulfate (MNPS) at the surface of a bilayer lipid membrane (BLM). We developed a theoretical model of this process describing the damage of MNPS coupled with the release of the protons at the membrane surface, as well as the exchange of MNPS molecules and protons between the membrane and solution. We found that the total change in the boundary potential difference across the membrane, ∆ϕ_b, is the sum of opposing effects of adsorption of MNPS anions and release of protons at the membrane–water interface. Steady-state change in the ∆ϕ_b due to protons decreased with the concentration of the buffer and increased with the pH of the solution. The change in the concentration of protons evaluated from measurements of ∆ϕ_b was close to that in the unstirred water layer near the BLM. This result, as well as rate constants of the proton exchange between the membrane and the bulk solution, indicated that the rate-limiting step of the proton surface to bulk release is the change in the concentration of protons in the unstirred layer. This means that the protons released from MNPS remain in equilibrium between the BLM surface and an adjacent water layer. Full article

Polymer ion-exchange membranes are featured in a variety of modern technologies including separation, concentration and purification of gases and liquids, chemical and electrochemical synthesis, and hydrogen power generation. In addition to transport properties, the strength, elasticity, and chemical stability of such materials are important characteristics for practical applications. Perfluorosulfonic acid (PFSA) membranes are characterized by an optimal combination of these properties. Today, one of the most well-known practical applications of PFSA membranes is the development of fuel cells. Some disadvantages of PFSA membranes, such as low conductivity at low humidity and high temperature limit their application. The approaches to optimization of properties are modification of commercial PFSA membranes and polymers by incorporation of different additive or pretreatment. This review summarizes the approaches to their modification, which will allow the creation of materials with a different set of functional properties, differing in ion transport (first of all proton conductivity) and selectivity, based on commercially available samples. These approaches include the use of different treatment techniques as well as the creation of hybrid materials containing dopant nanoparticles. Modification of the intrapore space of the membrane was shown to be a way of targeting the key functional properties of the membranes. Full article

ADAM17, a prominent member of the “Disintegrin and Metalloproteinase” (ADAM) family, controls vital cellular functions through the cleavage of transmembrane substrates, including epidermal growth factor receptor (EGFR) ligands such as transforming growth factor (TGF)-alpha and Epiregulin (EREG). Several ADAM17 substrates are relevant to oncogenesis and tumor growth. We have presented evidence that surface exposure of phosphatidylserine (PS) is pivotal for ADAM17 to exert sheddase activity. The scramblase Xkr8 is instrumental for calcium-independent exposure of PS in apoptotic cells. Xkr8 can be dually activated by caspase-3 and by kinases. In this investigation, we examined whether Xkr8 would modulate ADAM17 activity under apoptotic and non-apoptotic conditions. Overexpression of Xkr8 in HEK293T cells led to significantly increased caspase-dependent as well as PMA-induced release of EREG and TGF-alpha. Conversely, siRNA-mediated downregulation of Xkr8 in colorectal Caco-2 cancer cells led to decreased PS externalization upon induction of apoptosis, which was accompanied by reduced shedding of endogenously expressed EREG and reduced cell survival. We conclude that Xkr8 shares with conventional scramblases the propensity to upmodulate the ADAM-sheddase function. Liberation of growth factors could serve a rescue function in cells on the pathway to apoptotic death. Full article

N,N-dimethylformamide (DMF) has excellent chemical stability and is widely used as an aprotic polar solvent. In order to reduce production costs and reduce pollution to the surrounding environment, it is necessary to recycle and reuse DMF. Previous research has found that the thin film composite nanofiltration membrane prepared from liquefied walnut shells exhibited a high rejection rate in DMF, but relatively low permeance and mechanical strength. In order to increase permeance without compromising the separation performance, ethylenediamine (EDA) is used as a modifier to graft onto the structure of liquefied walnut shell through the Mannich reaction. Then, modified liquefied walnut shell as an aqueous monomer reacts with trimesoyl chloride (TMC) via the interfacial polymerization method on the EDA-crosslinked polyetherimide (PEI) membrane. The results show that the permeance of the prepared membrane is significantly improved by an order of magnitude, demonstrating a rejection rate of 98% for crystal violet (CV), and a permeance of 3.53 L m⁻² h⁻¹ bar⁻¹ in DMF. In conclusion, this study reveals the potential of utilizing liquefied walnut shells as raw materials for preparing high-performance separation membranes and demonstrates that surface modification is a feasible approach to enhance permeance of membranes without sacrificing the rejection rate. Full article

The goal of the current study is to enhance the hemocompatibility of polyethersulfone (PES) membranes using heparin immobilization. Heparin was immobilized covalently and via electrostatic interaction with the positively charged PES surface (pseudo-zwitterionic (pZW) complex) to investigate the influence of each method on the membrane hemocompatibility. In situ synchrotron radiation micro-computed tomography (SR-µCT) imaging, available at the Canadian Light Source (CLS), was used to critically assess the fibrinogen adsorption to the newly synthesized membranes qualitatively and quantitatively using an innovative synchrotron-based X-ray tomography technique. The surface roughness of the synthesized membranes was tested using atomic force microscopy (AFM) analysis. The membrane hemocompatibility was examined through the ex vivo clinical interaction of the membranes with patients’ blood to investigate the released inflammatory biomarkers (C5a, IL-1α, IL-1β, IL-6, vWF, and C5b-9). The presence and quantitative analysis of a stable hydration layer were assessed with DSC analysis. Surface modification resulted in reduced surface roughness of the heparin-PES membrane. Both types of heparin immobilization on the PES membrane surface resulted in a decrease in the absolute membrane surface charge from −60 mV (unmodified PES) to −13 mV for the pZW complex and −9.16 mV for the covalently attached heparin, respectively. The loss of human serum fibrinogen (FB) was investigated using UV analysis. The PES membrane modified with the heparin pseudo-ZW complex showed increased FB retention (90.5%), while the unmodified PES membrane and the heparin covalently attached PES membrane exhibited approximately the same level of FB retention (81.3% and 79.8%, respectively). A DSC analysis revealed an improvement in the content of the hydration layer (32% of non-freezable water) for the heparin-coated membranes compared to the unmodified PES membrane (2.84%). An SR-µCT analysis showed that the method of heparin immobilization significantly affects FB adsorption distribution across the membrane thickness. A quantitative analysis using SR-µCT showed that when heparin is attached covalently, FB tends to be deposited inside the membrane pores at the top (layer index 0–40) membrane regions, although its content peak distribution shifted to the membrane surface, whereas the unmodified PES membrane holds 90% of FB in the middle (layer index 40–60) of the membrane. The ex vivo hemocompatibility study indicates an improvement in reducing the von Willebrand factor (vWF) for the heparin pseudo-ZW PES membrane compared to the covalently attached heparin and the untreated PES. Full article