Track-etched Membranes Research Articles

A novel approach for extracting magnetic properties of double-shell nanotubes of Prussian blue and its Cr analog with the use of a mathematical hysteresis decomposition

This work presents the synthesis and investigation of Prussian blue and its chromium analog nanotubes obtained inside porous polycarbonate track etch (PCTE) membranes by electrochemical deposition. The process yielded nanotubes with outer diameters between 50 and 200 nm and thicknesses of approximately 30 nm. It was found that decreasing nanotube diameter had little or no effect on magnetic properties (critical temperature and coercivity). Additionally, the growing process and the basic properties of double-shell nanotubes are described. These double-shell structures show a two-component magnetic behavior. By using the theoretical model, it is possible to decompose the hysteresis loops into the base constituents and derive the relative concentration of each counterpart.

Eco-Friendly Electroless Template Synthesis of Cu-Based Composite Track-Etched Membranes for Sorption Removal of Lead(II) Ions

This paper reports the synthesis of composite track-etched membranes (TeMs) modified with electrolessly deposited copper microtubules using copper deposition baths based on environmentally friendly and non-toxic reducing agents (ascorbic acid (Asc), glyoxylic acid (Gly), and dimethylamine borane (DMAB)), and comparative testing of their lead(II) ion removal capacity via batch adsorption experiments. The structure and composition of the composites were investigated by X-ray diffraction technique and scanning electron and atomic force microscopies. The optimal conditions for copper electroless plating were determined. The adsorption kinetics followed a pseudo-second-order kinetic model, which indicates that adsorption is controlled by the chemisorption process. A comparative study was conducted on the applicability of the Langmuir, Freundlich, and Dubinin-Radushkevich adsorption models to define the equilibrium isotherms and the isotherm constants for the prepared composite TeMs. Based on the regression coefficients R2, it has been shown that the Freundlich model better describes the experimental data of the composite TeMs on the adsorption of lead(II) ions.

Electrochemical detection of lead and cadmium ions in water by sensors based on modified track-etched membranes

Electrochemical sensors based on PET track-etched membranes (TeMs) were prepared by photograft polymerization of 2-hydroxyethylmethacrylate (HEMA) and subsequent formation of interpolyelectrolyte complexes with poly(allylamine) (PAlAm). The functionalized TeMs were characterized by scanning electron microscopy (SEM), FTIR spectroscopy, gas permeability and colorimetric assay. Parameters of graft polymerization such as monomer concentration, time of irradiation, solvent and others were estimated and optimized. Cd(II) and Pb(II) ions were detected by using square wave anodic stripping voltammetry (SW-ASV). Additional modification of the modified membranes with 4-mercaptophenylboronic acid (MPBA) led to increasing of stability of the sensors. The linear range for the detection of Cd(II) and Pb(II) ions using the modified electrode was 50 µg - 4.25 mg/L and 10 µg – 4.25 mg/L. Moreover, the obtained results of SW-ASV demonstrated that the enhancement in the electrochemical signals was achieved with PET TeMs-g-PHEMA-PAlAm\MPBA compared to that of a bare PET TeMs-g-PHEMA. Selectivity test showed that alkali and alkaline earth metal ions, except for magnesium (up to 1 mg/l), do not particularly interfere with the determination of lead and cadmium in the analyte. Sensing of Pb and Cd ions in river water demonstrate us that prepared sensors can be used in real conditions with sufficient accuracy and reproducibility of the results.

Selective Separation of Singly Charged Chloride and Dihydrogen Phosphate Anions by Electrobaromembrane Method with Nanoporous Membranes.

The entrance of even a small amount of phosphorus compounds into natural waters leads to global problems that require the use of modern purification technologies. This paper presents the results of testing a hybrid electrobaromembrane (EBM) method for the selective separation of Cl- (always present in phosphorus-containing waters) and H2PO4- anions. Separated ions of the same charge sign move in an electric field through the pores of a nanoporous membrane to the corresponding electrode, while a commensurate counter-convective flow in the pores is created by a pressure drop across the membrane. It has been shown that EBM technology provides high fluxes of ions being separated across the membrane as well as a high selectivity coefficient compared to other membrane methods. During the processing of solution containing 0.05 M NaCl and 0.05 M NaH2PO4, the flux of phosphates through a track-etched membrane can reach 0.29 mol/(m2×h). Another possibility for separation is the EBM extraction of chlorides from the solution. Its flux can reach 0.40 mol/(m2×h) through the track-etched membrane and 0.33 mol/(m2×h) through a porous aluminum membrane. The separation efficiency can be very high by using both the porous anodic alumina membrane with positive fixed charges and the track-etched membrane with negative fixed charges due to the possibility of directing the fluxes of separated ions in opposite sides.

Hydrogen Isotope Separation Using Graphene-Based Membranes in Liquid Water.

Hydrogen isotope separation has been effectively achieved electrochemically by passage of gaseous H2/D2 through graphene/Nafion composite membranes. Nevertheless, deuteron nearly does not exist in the form of gaseous D2 in nature but as liquid water. Thus, it is a more feasible way to separate and enrich deuterium from water. Herein, we have successfully transferred monolayer graphene to a rigid and porous polymer substrate, PITEM (polyimide track-etched membrane), which could avoid the swelling problem of the Nafion substrate as well as keep the integrity of graphene. Meanwhile, defects in the large area of CVD graphene could be successfully repaired by interfacial polymerization resulting in a high separation factor. Moreover, a new model was proposed for the proton transport mechanism through monolayer graphene based on the kinetic isotope effect (KIE). In this model, graphene plays a significant role in the H/D separation process by completely breaking the O-H/O-D bond, which can maximize the KIE, leading to increased H/D separation performance. This work suggests a promising application for using monolayer graphene in the industry and proposes a pronounced understanding of proton transport in graphene.

Through-hole composite membrane with an ultrathin oxide shell for highly robust and transparent air filters

Exploring pore structures that are optically transparent and have high filtration efficiency for ultrafine dust is very important for realizing passive window filters for indoor air purification. Herein, a polyester track-etched (PETE) membrane with vertically perforated micropores is investigated as a cost-effective candidate for transparent window filters. The pore size, which governs transparency and filtration efficiency, can be precisely tuned by conformally depositing an ultrathin oxide layer on the PETE membrane via atomic layer deposition. The maximum visible light transmittance (∼81.2 %) was achieved with an alumina layer of approximately 55 nm, and the resulting composite membrane exhibited competitive filtration efficiency compared to commercial products. The chemically inert alumina layer also increased resistance to various external stimuli and enabled simple cleaning of the contaminated membrane surface with a solvent. The membrane installed on an insect screen effectively maintained its filtration performance (∼85 % for PM2.5) even after 10 reuse cycles under extremely harsh conditions (PM2.5 concentration: ∼5000 μg cm−3). The proposed through-hole composite membrane can expand the choice of aesthetic window filters to situations that require high outside visibility and daylighting.

Electric Discharge Synthesis of Colloidal Silver Nanoparticle Solutions Using Various Modifiers for Immobilization on the Surface of Track-Etched Membranes

Electric Discharge Synthesis of Colloidal Silver Nanoparticle Solutions Using Various Modifiers for Immobilization on the Surface of Track-Etched Membranes

A flow-based enzyme-free biosensor fabricated using track-etched membrane electrodes: Selective and sensitive detection of uric acid

A flow-based, enzyme-free biosensor for the selective and sensitive determination of uric acid was developed using track-etched membrane electrodes (TEMEs). The proposed sensor system comprises a pre-reactor electrode to decompose interfering species, such as L-ascorbic acid, and a detector electrode to detect uric acid. TEMEs were prepared by sputter deposition of gold on a track-etched membrane filter. Acetylene black (AB) was introduced as an electrode catalyst by simple filtration with the TEME, and the sensitivity for uric acid using the AB-decorated Au-TEME was much greater than that with bare Au-TEME. The insertion of the 2-aminoethanethiol-modified Au-TEMEs as pre-reactor electrodes upstream of the AB-decorated detector electrode eliminated the interference caused by the co-existence of L-ascorbic acid because the interfering species were electrolyzed at the pre-reactor electrode prior to detection of uric acid. The proposed sensor system was incorporated into a flow-injection analysis system to evaluate the sensor performance. The detection limit of uric acid was 0.6 μM. A recovery test by standard addition to human urine samples also showed satisfactory results.

Porous honeycomb film membranes enhance endothelial barrier integrity in human vascular wall bilayer model compared to standard track-etched membranes.

In vitro vascular wall bilayer models for drug testing and disease modeling must emulate the physical and biological properties of healthy vascular tissue and its endothelial barrier function. Both endothelial cell (EC)-vascular smooth muscle cell (SMC) interaction across the internal elastic lamina (IEL) and blood vessel stiffness impact endothelial barrier integrity. Polymeric porous track-etched membranes (TEM) typically represent the IEL in laboratory vascular bilayer models. However, TEM stiffness exceeds that of diseased blood vessels, and the membrane pore architecture limits EC-SMC interaction. The mechanical properties of compliant honeycomb film (HCF) membranes better simulate the Young's modulus of healthy blood vessels, and HCFs are thinner (4 vs. 10 μm) and more porous (57 vs. 6.5%) than TEMs. We compared endothelial barrier integrity in vascular wall bilayer models with human ECs and SMCs statically cultured on opposite sides of HCFs and TEMs (5 μm pores) for up to 12 days. Highly segregated localization of tight junction (ZO-1) and adherens junction (VE-cadherin) proteins and quiescent F-actin cytoskeletons demonstrated superior and earlier maturation of interendothelial junctions. Quantifying barrier integrity based on transendothelial electrical resistance (TEER), membranes showed only minor but significant TEER differences despite enhanced junctional protein localization on HCF. Elongated ECs on HCF likely experienced greater paracellular diffusion than blocky ECs on TEM. Also, larger populations of plaques of connexin 43 subunit-containing gap junctions suggested enhanced EC-SMC communication across the more porous, thinner HCF. Compared with standard TEMs, engineered vascular wall bilayers cultured on HCFs better replicate physiologic endothelial barrier integrity.

Experimental and theoretical retentions of sub-10 nm colloidal nanoparticles by large-pore ultrafiltration membranes in isopropanol and water

Effective removal of small colloidal nanoparticles (NPs, e.g., <20 nm), including rigid particles, macromolecules, organics, viruses, antibiotics, hormones, etc., by dead-end filtration, is very important in drinking water, chemical, biopharmaceutical, and semiconductor factories. Most existing operations focused on sieving mechanism-based filtration with small-pore membranes (e.g., <20 nm) to capture these tiny NPs, which unfortunately leads to high energy consumption. This study proposed an emerging method that is to use large pore membranes (i.e., ∼100 nm) to capture NPs down to 2.8 nm. The ultimate goal is to address the grand challenge presented in the United Nations Sustainable Development Goal 12 on energy saving. To capture (or adhere) small NPs by large-pore membranes, the surface electrostatic interactions between NP and membrane should be considered in addition to the sieving mechanism. To examine the feasibility of the proposed method, the retention efficiency of ∼100 nm rated polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polycarbonate track-etched (PCTE, as a model filter) membranes against 2.8 nm ZnS quantum dot (QD), 5 and 10 nm Au and 100 nm PSL in water and isopropanol (IPA, a representative organic solvent) were studied experimentally and theoretically. In the experiments, the electrospray-scanning mobility particle sizer (ES-SMPS) was used to measure the size distribution of these nanosized colloids before and after the membrane to determine the retention efficiency. In the theory, we combined the hydrodynamic particle transport, extended Derjaguin-Landau-Verwey-Overbeek (xDLVO), and Maxwell models to calculate the NP retention. Results showed that the data agreed with the theoretical model very well, and the NP retentions in IPA were higher than that in water due to a significant change of acid-base interaction from repulsion to attraction. The retention of the 10 nm Au NPs and the 2.8 nm NPs could be attained by ∼80 and 35%, respecively, in IPA by the PTFE. This study was the first to show the combined theoretical model can accurately predict the retention of sub-10 nm NPs by different membranes in an organic solvent and water. The model predicts the retention of 5 nm Au NPs can be increased to higher than 99% by increasing the zeta potential of the PTFE about 5 times, thus a sustainable UF cutting significant carbon footprint is foreseeable in near future.

Aptasensors based on track-etched membranes coated with nanostructured silver layer for influenza A and B virus detection

A biosensor based on a polyethylene terephthalate track membrane coated with silver nanoparticles is proposed for the detection of influenza A and B viruses using aptamers for specific sorption of the viruses on the membrane surface, as well as for the introduction of a Raman-active or fluorescent label in the complex. The analytical signal was recorded using a Raman spectrometer, observing the effects of surface-enhancing of the intensity of optical responses from the labels.

Aptasensors Based on Track-Etched Membranes Coated with a Nanostructured Silver Layer for Influenza A and B Virus Detection

Aptasensors Based on Track-Etched Membranes Coated with a Nanostructured Silver Layer for Influenza A and B Virus Detection

Low-density Pt nanoarray-based hydrogen peroxide sensing platform and its application in trace sarcosine detection

Hydrogen peroxide (H2O2) is an important signaling molecule that regulates many biological processes. It is of great value to realize rapid, accurate, highly sensitive and low-cost H2O2 detection in the immediate detection of trace disease markers. Low-density nanoelectrode arrays have a high signal-to-noise ratio and are advantageous for trace detection. In this paper, low-density Pt nanoelectrode arrays were successfully prepared by a simple method of ion sputtering combined with electrodeposition based on a track-etched polycarbonate membrane template. The arrays had a detection limit as low as 0.03 μM for H2O2 at a constant potential, a sensitivity of 125.9 μA mM−1, and a linear range spanning nearly four orders of magnitude (0.1–655 μM). The developed sarcosine sensors based on these arrays had a very low detection limit (0.08 μM) and wide linear range (0.5–64.5 μM) for the rapid detection of trace amounts of sarcosine in serum. With a wide linear range and low detection limits, this hydrogen peroxide sensing platform has great potential for use in the rapid electrochemical detection of trace substances.

Aptamer-coated track-etched membranes with a nanostructured silver layer for single virus detection in biological fluids.

Aptasensors based on surface-enhanced Raman spectroscopy (SERS) are of high interest due to the superior specificity and low limit of detection. It is possible to produce stable and cheap SERS-active substrates and portable equipment meeting the requirements of point-of-care devices. Here we combine the membrane filtration and SERS-active substrate in the one pot. This approach allows efficient adsorption of the viruses from the solution onto aptamer-covered silver nanoparticles. Specific determination of the viruses was provided by the aptamer to influenza A virus labeled with the Raman-active label. The SERS-signal from the label was decreased with a descending concentration of the target virus. Even several virus particles in the sample provided an increase in SERS-spectra intensity, requiring only a few minutes for the interaction between the aptamer and the virus. The limit of detection of the aptasensor was as low as 10 viral particles per mL (VP/mL) of influenza A virus or 2 VP/mL per probe. This value overcomes the limit of detection of PCR techniques (∼103 VP/mL). The proposed biosensor is very convenient for point-of-care applications.

Electron transparent nanotubes reveal crystallization pathways in confinement.

The cylindrical pores of track-etched membranes offer excellent environments for studying the effects of confinement on crystallization as the pore diameter is readily varied and the anisotropic morphologies can direct crystal orientation. However, the inability to image individual crystals in situ within the pores in this system has prevented many of the underlying mechanisms from being characterized. Here, we study the crystallization of calcium sulfate within track-etched membranes and reveal that oriented gypsum forms in 200 nm diameter pores, bassanite in 25-100 nm pores and anhydrite in 10 nm pores. The crystallization pathways are then studied by coating the membranes with an amorphous titania layer prior to mineralization to create electron transparent nanotubes that protect fragile precursor materials. By visualizing the evolutionary pathways of the crystals within the pores we show that the product single crystals derive from multiple nucleation events and that orientation is determined at early reaction times. Finally, the transformation of bassanite to gypsum within the membrane pores is studied using experiment and potential mean force calculations and is shown to proceed by localized dissolution/reprecipitation. This work provides insight into the effects of confinement on crystallization processes, which is relevant to mineral formation in many real-world environments.

Environmentally friendly loading of palladium nanoparticles on nanoporous PET track-etched membranes grafted by poly(1-vinyl-2-pyrrolidone) via RAFT polymerization for the photocatalytic degradation of metronidazole.

Nanoporous track-etched membranes (TeMs) are highly versatile materials that have shown promise in various applications such as filtration, separation, adsorption, and catalysis due to their mechanical integrity and high surface area. The performance of TeMs as catalysts for removing toxic pollutants is greatly influenced by the pore diameter, density, and functionalization of the nanochannels. In this study, the synthesis of functionalized poly(ethylene terephthalate) (PET) TeMs with Pd nanoparticles (NPs) as catalysts for the photodegradation of the antibiotic metronidazole (MTZ) was methodically investigated and their catalytic activity under UV irradiation was compared. Before loading of the Pd NPs, the surface and nanopore walls of the PET TeMs were grafted by poly(1-vinyl-2-pyrrolidone) (PVP) via UV-initiated reversible addition fragmentation chain transfer (RAFT)-mediated graft copolymerization. The use of RAFT polymerization allowed for precise control over the degree of grafting and graft lengths within the nanochannels of PVP grafted PET TeMs (PVP-g-PET). Pd NPs were then loaded onto PVP-g-PET using several environmentally friendly reducing agents such as ascorbic acid, sodium borohydride and a plant extract. In addition, a conventional thermal reduction technique was also applied for the reduction of the Pd NPs. The grafting process created a surface with high-sorption capacity for MTZ and also high stabilizing effect for Pd NPs due to the functional PVP chains on the PET substrate. The structure and composition of the composite membranes were elucidated by scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, thermogravimetry, contact angle measurements and energy dispersive X-ray (EDX), X-ray photoelectron (XPS) and Fourier transform infra-red (FTIR) spectroscopies. The effects of different types of reducing agents, pH, the amount of loaded catalyst and MTZ concentration on the MTZ catalytic degradation efficiency of the obtained composites were investigated. The efficiency of the catalyst prepared in the presence of ascorbic acid was superior to the others (89.86% removal at 30 mg L-1 of MTZ). Maximum removal of MTZ was observed at the natural pH (6.5) of the MTZ solution at a concentration of 30 mg per L MTZ. The removal efficiency was decreased by increasing the catalyst dosage and the initial MTZ concentration. The reaction rate constant was reduced from 0.0144 to 0.0096 min-1 by increasing the MTZ concentration from 20 to 50 mg L-1. The photocatalyst revealed remarkable photocatalytic activity even after 10 consecutive cycles.

Preparation of Poly(Ethylene Terephthalate) Track-Etched Membranes for the Separation of Water-Oil Emulsions

Rapid industrial growth in the petrochemical, pharmaceutical, metallurgical and food industries, as well as stormwater that accumulates pollution from the roadway and the territories of motor transport enterprises, gas stations, car washes and other municipal services have led to the formation of a large amount of oily wastewater. Oil-containing wastewater is a multicomponent, multiphase water system and, as a rule, is in a state stabilized by various factors, which greatly complicates their processing. Pollution of water sources with oil-containing compounds leads to negative consequences for both living organisms and human health. Therefore, the need to treat oily wastewater is an urgent problem. In this article, poly(ethylene terephthalate) track-etched membranes (PET TeMs) with pore diameters of ~ 5.1 μm and pore density of 1∙106 pore/cm2 were modified by formation of polyelectrolyte complexes of PET TeMs surface with poly(allylamine) (PAAm) and tested for oil-water separation by using hexadecane/water (at pH=2) and chloroform/water (at pH=2) emulsions. Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM), energy dispersive X-ray (EDX) analysis, contact angle measurements were used for membrane characterization. The efficiency of oil-water separation was evaluated by flux measurements. Results showed separation performance of 267 mL/m2·s for hexadecane/water (pH=2) and 100 mL/m2·s for chloroform/water (pH=2) at vacuum pressure of 700 mbar.

Ultralarge suspended and perforated graphene membranes for cell culture applications.

With its high mechanical strength and its remarkable thermal and electrical properties, suspended graphene has long been expected to find revolutionary applications in optoelectronics or as a membrane in nano-devices. However, the lack of efficient transfer and patterning processes still limits its potential. In this work, we report an optimized anthracene-based transfer process to suspend few layers of graphene (1-, 2- and 4-layers) in the millimeter range (up to 3 mm) with high reproducibility. We have explored the advantages and limitations for patterning of these membranes with micrometer-resolution by focused ion beam (FIB) and picosecond pulsed laser ablation techniques. The FIB approach offers higher patterning resolution but suffers from the low throughput. We demonstrate that cold laser ablation is a fast and flexible method for micro-structuring of suspended graphene. One promising field of application of ultimately thin, microporous graphene membranes is their use as next-generation cell culture supports as alternative to track-etched polymer membranes, which often exhibit poor permeability and limited cell-to-cell communication across the membranes. To this end, we confirmed good adhesion and high viability of placental trophoblast cells cultivated on suspended porous graphene membranes without rupturing of the membranes. Overall, there is high potential for the further development of ultrathin suspended graphene membranes for many future applications, including their use for biobarrier cell culture models to enable predictive transport and toxicity assessment of drugs, environmental pollutants, and nanoparticles.

Open multi-organ communication device for easy interrogation of tissue slices.

Here, we have developed an open multi-organ communication device that facilitates cellular and molecular communication between ex vivo organ slices. Measuring communication between organs is vital for understanding the mechanisms of health regulation yet remains difficult with current technology. Communication between organs along the gut-brain-immune axis is a key regulator of gut homeostasis. As a novel application of the device, we have used tissue slices from the Peyer's patch (PP) and mesenteric lymph node (MLN) due to their importance in gut immunity; however, any organ slices could be used here. The device was designed and fabricated using a combination of 3D printed molds for polydimethylsiloxane (PDMS) soft lithography, PDMS membranes, and track-etch porous membranes. To validate cellular and protein transfer between organs on-chip, we used fluorescence microscopy to quantitate movement of fluorescent proteins and cells from the PP to the MLN, replicating the initial response to immune stimuli in the gut. IFN-γ secretion during perfusion from a naïve vs. inflamed PP to a healthy MLN was quantitated to demonstrate soluble signaling molecules are moving on-chip. Finally, transient catecholamine release was measured during perfusion from PP to MLN using fast-scan cyclic voltammetry at carbon-fiber microelectrodes to demonstrate a novel application of the device for real-time sensing during communication. Overall, we show an open-well multi-organ device capable of facilitating transfer of soluble factors and cells with the added benefit of being available for external analysis techniques like electrochemical sensing which will advance abilities to probe communication in real-time across multiple organs ex vivo.

Формирование на поверхности трековых мембран гидрофобных покрытий методом магнетронного распыления полимеров в вакууме

The surface properties and chemical structure of nanoscale coatings deposited on the poly(ethylene terephthalate) track-etched membranes surface by magnetron sputter deposition of ultra-high molecular weight polyethylene and polytetrafluoroethylene in vacuum are studied. It is shown that the application of coatings leads to hydrophobization of membrane surface, the degree of which depends on the type of polymer used for sputtering and the thickness of the coating. It is established that the use of this modification method leads to smoothing of structural inhomogeneities of the membrane surface layer. This result is explained by the deposition of coatings in the pore channels at a certain depth from the entrance and the overlap of pores on the surface of modified membranes. Besides, the deposition of coatings on the track-etched membrane surface leads to a change in the pore shape. The diameter of the pores on the untreated side of the membranes remains unchanged and decreases significantly on the modified side. The pores of the membranes acquire an asymmetric (conical) shape in this case. The study of the chemical structure of coatings by X-ray photoelectron spectroscopy showed that they contain oxygen-containing functional groups due to the oxidation of the polymer matrix. The developed composite membranes can be used in the membrane distillation processes for the desalination of seawater.