Track-etched Membranes Research Articles

Detection behavior of phenolic compounds in a dual-electrode system assembled from track-etched membrane electrodes

Detection behavior of phenolic compounds in a dual-electrode system assembled from track-etched membrane electrodes

Biofabrication, biochemical profiling, and in vitro applications of salivary gland decellularized matrices via magnetic bioassembly platforms.

Trending three-dimensional tissue engineering platforms developed via biofabrication and bioprinting of exocrine glands are on the rise due to a commitment to organogenesis principles. Nevertheless, a proper extracellular matrix (ECM) microarchitecture to harbor primary cells is yet to be established towards human salivary gland (SG) organogenesis. By using porcine submandibular gland (SMG) biopsies as a proof-of-concept to mimic the human SG, a new decellularized ECM bioassembly platform was developed herein with varying perfusions of sodium dodecyl sulfate (SDS) to limit denaturing events and ensure proper preservation of the native ECM biochemical niche. Porcine SMG biopsies were perfused with 0.01%, 0.1%, and 1% SDS and bio-assembled magnetically in porous polycarbonate track-etched (PCTE) membrane. Double-stranded DNA (dsDNA), cell removal efficiency, and ECM biochemical contents were analyzed. SDS at 0.1% and 1% efficiently removed dsDNA (< 50ng/mg) and preserved key matrix components (sulfated glycosaminoglycans, collagens, elastin) and the microarchitecture of native SMG ECM. Bio-assembled SMG decellularized ECM (dECM) perfused with 0.1-1% SDS enhanced cell viability, proliferation, expansion confluency rates, and tethering of primary SMG cells during 7 culture days. Perfusion with 1% SDS promoted greater cell proliferation rates while 0.1% SDS supported higher acinar epithelial expression when compared to basement membrane extract and other substrates. Thus, this dECM magnetic bioassembly strategy was effective for decellularization while retaining the original ECM biochemical niche and promoting SMG cell proliferation, expansion, differentiation, and tethering. Altogether, these outcomes pave the way towards the recellularization of this novel SMG dECM in future in vitro and in vivo applications.

Modeling the Conductivity and Diffusion Permeability of a Track-Etched Membrane Taking into Account a Loose Layer.

The microheterogeneous model makes it possible to describe the main transport properties of ion-exchange membranes using a single set of input parameters. This paper describes an adaptation of the microheterogeneous model for describing the electrical conductivity and diffusion permeability of a track-etched membrane (TEM). Usually, the transport parameters of TEMs are evaluated assuming that ion transfer occurs through the solution filling the membrane pores, which are cylindrical and oriented normally to the membrane surface. The version of the microheterogeneous model developed in this paper takes into account the presence of a loose layer, which forms as an intermediate layer between the pore solution and the membrane bulk material during track etching. It is assumed that this layer can be considered as a "gel phase" in the framework of the microheterogeneous model due to the fixed hydroxyl and carboxyl groups, which imparts ion exchange properties to the loose layer. The qualitative and quantitative agreement between the calculated and experimental concentration dependencies of the conductivity and diffusion permeability is discussed. The role of the model input parameters is described in relation to the structural features of the membrane. In particular, the inclination of the pores relative to the surface and their narrowing in the middle part of the membrane can be important for their properties.

Electrodeposited magnetic nanoporous membrane for high-yield and high-throughput immunocapture of extracellular vesicles and lipoproteins.

Superparamagnetic nanobeads offer several advantages over microbeads for immunocapture of nanocarriers (extracellular vesicles, lipoproteins, and viruses) in a bioassay: high-yield capture, reduction in incubation time, and higher capture capacity. However, nanobeads are difficult to "pull-down" because their superparamagnetic feature requires high nanoscale magnetic field gradients. Here, an electrodeposited track-etched membrane is shown to produce a unique superparamagnetic nano-edge ring with multiple edges around nanopores. With a uniform external magnetic field, the induced monopole and dipole of this nano edge junction combine to produce a 10× higher nanobead trapping force. A dense nanobead suspension can be filtered through the magnetic nanoporous membrane (MNM) at high throughput with a 99% bead capture rate. The yield of specific nanocarriers in heterogeneous media by nanobeads/MNM exceeds 80%. Reproducibility, low loss, and concentration-independent capture rates are also demonstrated. This MNM material hence expands the application of nanobead immunocapture to physiological samples.

Transmission of poly(dT60 ) single-stranded DNA through polycarbonate track-etched ultrafiltration membranes.

The objective of this study was to examine membrane filtration of a single stranded DNA (ssDNA) with 60 thymine nucleotides, and to elucidate the variables controlling its transmission across track-etched porous membranes. Dead end filtration measurements were performed using different pore size membranes (10, 15, and 30 nm) at different transmembrane pressures in solutions with ionic strength ranging from 0 to 1000 mM NaCl. The diffusivity of the ssDNA was determined using fluorescence recovery after photobleaching, yielding hydrodynamic radii ranging from 1.6 to 2.8nm, with values decreasing with increasing solution ionic strength. Despite the small ssDNA/membrane pore size, nearly 100% rejection was observed for measurements performed with the 10 and 15 nm pore size membranes under low-ionic strength conditions. These high rejections can be attributed to strong repulsive electrostatic ssDNA-membrane interactions. With increasing ionic strength, electrostatic interactions as well as the effective size of the ssDNA decreases and the flexibility of the ssDNA increases, leading to a reduction in ssDNA rejection. A design of experiments approach was used to plan filtration experiments that adequately covered the variable space with a manageable number of experiments. The results yielded an empirical expression relating ssDNA rejection to pore size, solution ionic strength and transmembrane pressure. There was evidence of flow induced elongation at high-transmembrane pressures in the 30 nm pore size membranes, but not in the smaller pore size membranes. These results are consistent with critical flux estimates developed using a free draining model for the ssDNA.

Pore Filled Ion-Conducting Materials Based on Track-Etched Membranes and Sulfonated Polystyrene

Synthesis of proton-conducting materials based on track-etched membranes from polyvinylidene fluoride and sulfonated cross-linked polystyrene is described. The synthesis has been carried out by filling the pores of the original or gamma-irradiated track-etched membrane by copolymerization of styrene/divinylbenzene followed by sulfonation of polystyrene with chlorosulfonic acid. The resulting membranes have been studied by scanning electron microscopy and ATR IR spectroscopy. Membrane ionic conductivity, hydrogen gas permeability, ion-exchange capacity, and water absorption were measured. The ionic conductivity at 30°C reaches 51.7 mS/cm, which is almost three times higher than for Nafion®212 membranes; however, the gas permeability of the obtained materials also increases simultaneously.

Selective Trapping of Living Cells into Micropores within a Track-etched Membrane by Dielectrophoresis

In this study, an insulator-based dielectrophoresis device using a track-etched membrane was developed for selective trapping of living yeast cells. A high electric field was formed in cylindrical pores of 8-µm diameter within the insulating membrane between two transparent plate electrodes. At a frequency of 20 MHz, only a living cell could be drawn into the pore and trapped strongly by dielectrophoresis. For non-spherical cells with a diameter and length of 5 µm and 14 µm, respectively, it was found that a cell longer than the pore diameter was drawn into the pores with electro-orientation if the minor axis of the cell was shorter.

The Influence of Mechanical Stress Micro Fields around Pores on the Strength of Elongated Etched Membrane.

The investigation of the mechanical properties of polymer track-etched membranes (TMs) has attracted significant attention in connection with the extended region of their possible applications. In the present work, the mechanical stress fields around the pores of an elongated polyethylene terephthalate TM and around the 0.3 mm holes in model polymer specimens were studied in polarized light and with the finite element method. A break-up experiment showed the controlling role of stress field interaction in the forming of a microcrack system and the generation of a main crack with rupture of the TM (or model pattern). This interaction depended on the relative distance between the pores (holes) and their orientation. The results of the calculations of the pore distribution function over the surface of the TM via the net method and wavelet analysis are presented. The fractal character of pore distribution was established. The geometric characteristics of the TM pore system as initial defects are inherited by obtaining TM-based composites.

A wound dressing based on a track-etched membrane modified by a biopolymer nanoframe: physicochemical and biological characteristics

Ion track membranes (TMs) are obtained by irradiating thin polymer films, which are usually composed of polycarbonate and polyethylene terephthalate (PET). In medicine and biology, TMs are used for the filtration and separation of molecules and cells in addition to studies of cell migration, intercellular interactions, cell proliferation, and differentiation processes. However, the possibilities and prospects of using TMs as components of wound dressings have not been sufficiently explored. In our study, TMs composed of PET were tested since this material is biocompatible and used in prosthetics and reconstructive surgery. The method of combining TM and electroforming nanofibers, which we used in this study, is relatively new and still requires additional research.Thus, it was found that the main structural elements of the TM surface covered with a biolayer of a mixture of collagen and chitosan are fibers. Coating the TM with a bio-layer preserves its gas and water permeabilities. By varying the fixation method of the biopolymer layer, it is possible to regulate the physicochemical and biological functional properties of the wound dressing. The combination of the high biocompatibility of natural polymers and the stability of synthetic materials can be a successful strategy in manufacturing wound dressings of a new type with specified functional properties. Ion-track PET membranes with applied electrospun fibers from a mixture of chitosan and collagen can be used to produce the wound dressing.Abbreviated title: A wound dressing based on a track-etched membrane.

Switchable Ion Current Saturation Regimes Enabled via Heterostructured Nanofluidic Devices Based on Metal-Organic Frameworks.

The use of track-etched membranes allows further fine-tuning of transport regimes and thus enables their use in (bio)sensing and energy-harvesting applications, among others. Recently, metal-organic frameworks (MOFs) have been combined with such membranes to further increase their potential. Herein, the creation of a single track-etched nanochannel modified with the UiO-66 MOF is proposed. By the interfacial growth method, UiO-66-confined synthesis fills the nanochannel completely and smoothly, yet its constructional porosity renders a heterostructure along the axial coordinate of the channel. The MOF heterostructure confers notorious changes in the transport regime of the nanofluidic device. In particular, the tortuosity provided by the micro- and mesostructure of UiO-66 added to its charged state leads to iontronic outputs characterized by an asymmetric ion current saturation for transmembrane voltages exceeding 0.3V. Remarkably, this behavior can be easily and reversibly modulated by changing the pH of the media and it can also be maintained for a wide range of KCl concentrations. In addition, it is found that the modified-nanochannel functionality cannot be explained by considering just the intrinsic microporosity of UiO-66, but rather the constructional porosity that arises during the MOF growth process plays a central and dominant role.

Integration of enzyme-encapsulated mesoporous silica between nanohole array electrode and hydrogel film for flow-type electrochemical biosensor.

We herein propose a simple and sensitive electrochemical flow biosensor platform without an external flow device. The sensing unit comprises a platinum nanohole array electrode deposited on a nanoporous track-etched membrane (PtNH/NPM), a packed-layer of glucose oxidase-encapsulated mesoporous silica particles (GOD/MPS), and bovine serum albumin hydrogel film (BSA gel film). This sensing unit was fixed at the open window at the side of the plastic container with internal solution containing NaCl as osmotic reagent. When the sample glucose solution (0.10mL) was pipetted at the sensing unit, a portion of the sample solution (5 μL) was spontaneously transferred into the BSA gel film. The concentration gradient of NaCl between the internal solution and the BSA gel film induced osmotic flow of water toward the internal solution. This osmotic flow assisted delivery of glucose to the GOD/MPS and enzymatically generated H2O2 to the PtNH/NPM. The proposed sensor could be used repeatedly and produced a linear current response for glucose, with a limit of detection of 16μM. These sensor performances confirmed availability of the sensor design utilizing the osmotic flow.

Can Hindered Transport Models for Rigid Spheres Predict the Rejection of Single Stranded DNA from Porous Membranes?

In this paper, predictions from a theoretical model describing the rejection of a rigid spherical solute from porous membranes are compared to experimental results for a single stranded DNA (ssDNA) with 60 thymine nucleotides. Experiments were conducted with different pore size track-etched membranes at different transmembrane pressures and different NaCl concentrations. The model includes both hydrodynamic and electrostatic solute-pore wall interactions; predictions were made using different size parameters for the ssDNA (radius of gyration, hydrodynamic radius, and root mean square end-to-end distance). At low transmembrane pressures, experimental results are in good agreement with rejection predictions made using the hard sphere model for the ssDNA when the solute size is described using its root mean square end-to-end distance. When the ssDNA size is characterized using the radius of gyration or the hydrodynamic radius, the hard sphere model under-predicts rejection. Not surprisingly, the model overestimates ssDNA rejection at conditions where flow induced elongation of the DNA is expected. The results from this study are encouraging because they mean that a relatively simple hindered transport model can be used to estimate the rejection of a small DNA from porous membranes.

Characterization of the surface charge property and porosity of track-etched polymer membranes.

As an important property of porous membranes, the surface charge property determines many ionic behaviors of nanopores, such as ionic conductance and selectivity. Based on the dependence of electric double layers on bulk concentrations, ionic conductance through nanopores at high and low concentrations is governed by the bulk conductance and surface charge density, respectively. Here, through the investigation of ionic conductance inside track-etched single polyethylene terephthalate (PET) nanopores under various concentrations, the surface charge density of PET membranes is extracted as ∼-0.021C/m2 at pH 10 over measurements with 40 PET nanopores. Simulations show that surface roughness can cause underestimation in surface charge density due to the inhibited electroosmotic flow. Then, the averaged pore size and porosity of track-etched multipore PET membranes are characterized by the developed ionic conductance method. Through coupled theoretical predictions in ionic conductance under high and low concentrations, the averaged pore size and porosity of porous membranes can be obtained simultaneously. Our method provides a simple and precise way to characterize the pore size and porosity of multipore membranes, especially for those with sub-100nm pores and low porosities.

Functionalized silica nanoparticles coupled with nanoporous membrane for efficient ionic current rectification

In the last few decades, tremendous effort has been dedicated to mimicking the efficient ionic current rectification (ICR) of biological nanopores. Nanoporous membranes and singular nanopores with ICR functionality have been fabricated using advanced, yet costly technologies. We herein demonstrate that a simple, novel, and robust ICR platform can be constructed using 80 nm silica nanoparticles and a piece of 15 nm track-etched polycarbonate membrane. Efficient ICR can be obtained when voltages of different polarities are applied across the membrane, due to the asymmetric electrophoretic migration of silica nanoparticles whose surfaces are modified with different functional groups. The effect of pore size, ionic strength, pH, voltage magnitude, and density of silica nanoparticles on the efficiency of the ICR system has been systematically investigated in this report. Our results clearly show that smaller pore, lower ionic strength, appropriate pH value, higher electrical field strength, lower density of silica nanoparticles can generally enhance the efficiency of the ICR system. The principles of this new ICR system may find many potential applications in controllable drug delivery, energy storage and water purification.

Precise Pore Size Tailoring and Surface Chemistry Modification of Polycarbonate Membranes Using Atomic Layer Deposition

Physical and chemical surface modifications are commonly used in many applications such as energy generation and storage, microelectronics, water purification, gas separation, and medical/plant biology. In recent several years, sequential infiltration synthesis (SIS), a variant of atomic layer deposition (ALD), has emerged as a promising technology that uses self-limiting reactions to create hybrid organic/inorganic materials within the polymer-free volume. Herein, we employed ALD/SIS of Al2O3, SnO2, Ga2O3, TiO2, and In2O3 to precisely tune the pore size and surface characteristics of track-etched polycarbonate membranes. We used in situ Fourier transform infrared spectroscopy to elucidate the chemistry for Al2O3 SIS in polycarbonate and in situ quartz crystal microbalance measurements to probe the extent of Al2O3 infiltration during SIS in polycarbonate thin films. Next, we used scanning electron microscopy, thermogravimetric analysis, and water permeance measurements to probe the pore size reduction and conformality of SIS Al2O3 in the track-etched polycarbonate membranes. We then used water permeance measurements to compare the water flux for a series of membranes with similar pore size but different pore wall chemistry and compared these results with water contact angle measurements. Interestingly, the hydrophilic metal oxide coatings yielded higher water flux values compared to hydrophobic coatings. Finally, we examined ion-selective transport in the modified track-etched polycarbonate membranes and rationalized the results using zeta potential measurements of the ALD metal oxides. Keywords: atomic layer deposition; sequential infiltration synthesis; metal oxides; hydrophilicity/hydrophobicity; permeability; surface charge; ion conductivity/selectivity.

Hybrid PET Track-Etched Membranes Grafted by Well-Defined Poly(2-(dimethylamino)ethyl methacrylate) Brushes and Loaded with Silver Nanoparticles for the Removal of As(III).

Nanoporous track-etched membranes (TeM) are promising materials as adsorbents to remove toxic pollutants, but control over the pore diameter and density in addition to precise functionalization of nanochannels is crucial for controlling the surface area and efficiency of TeMs. This study reported the synthesis of functionalized PET TeMs as high-capacity sorbents for the removal of trivalent arsenic, As(III), which is more mobile and about 60 times more toxic than As(V). Nanochannels of PET-TeMs were functionalized by UV-initiated reversible addition fragmentation chain transfer (RAFT)-mediated grafting of 2-(dimethyamino)ethyl methacrylate (DMAEMA), allowing precise control of the degree of grafting and graft lengths within the nanochannels. Ag NPs were then loaded onto PDMAEMA-g-PET to provide a hybrid sorbent for As(III) removal. The As(III) removal efficiency of Ag@PDMAEMA-g-PET, PDMAEMA-g-PET, and pristine PET TeM was compared by adsorption kinetics studies at various pH and sorption times. The adsorption of As(III) by Ag@DMAEMA-g-PET and DMAEMA-g-PET TeMs was found to follow the Freundlich mechanism and a pseudo-second-order kinetic model. After 10 h, As(III) removal efficiencies were 85.6% and 56% for Ag@PDMAEMA-g-PET and PDMAEMA-g-PET, respectively, while PET template had a very low arsenic sorption capacity of 17.5% at optimal pH of 4.0, indicating that both PDMAEMA grafting and Ag-NPs loading significantly increased the As(III) removal capacity of PET-TeMs.

One-Dimensional Assemblies of Co3O4 Nanoparticles Formed from Cobalt Hydroxide Carbonate Prepared by Bio-Inspired Precipitation within Confined Space

Nanostructured spinel-type cobalt(II,III) oxide (Co3O4) finds applications in a wide range of technological fields including clean energy conversion systems and electrochemical devices. Low-dimensional morphologies have been identified as particularly promising for the optimization of transport characteristics and the design of anisometric building blocks for the controlled assembly into higher order superstructures. We here introduce a facile bio-inspired room-temperature approach to direct precipitation of one-dimensional basic cobalt carbonate as a precursor to Co3O4 by combining confined submicrometer reaction environments with a carboxylated structure-directing polyelectrolyte. Variation of the polymer concentration and molecular weight then affords control over the mode of infiltration into cylindrical track-etch membrane pores. While a high concentration of the polyelectrolyte additive induces the formation of high aspect ratio smooth fibers with a length resembling the entire pore volume, shorter porous rods with a needle-like substructure are deposited at low polymer concentrations or higher molecular weights. The generality of the infiltration mechanism is demonstrated by gradual substitution of Co2+ ions by Mn2+. Calcination pseudomorphically transforms the resulting intramembrane basic cobalt and manganese carbonate rods and fibers into hierarchical one-dimensional oxides with a porous nanoparticle-based mesostructure.

Rapid isolation and cryo-EM characterization of synaptic vesicles from mammalian brain.

Synaptic vesicles (SVs) store and release neurotransmitters at chemical synapses. Precise regulation of SV trafficking, exocytosis and endocytosis is crucial for neural transmission. Biochemical characterization of SVs, which is essential for research into neurotransmitter uptake and release, requires effective in vitro isolation methods. Here, we describe an improved and simple purification protocol for isolating SVs from mouse brain within 6 h, achieving a yield of approximately 0.4 mg of SVs per single brain. The use of track-etch membrane filtration and iodixanol cushion ensured the uniform morphology of SVs and low contaminants in the sample. Cryo-electron microscopy was used to show that the in vitro isolated SVs retained intact membrane-associated proteins, and observation of SVs in hippocampal neurons using cryo-electron tomography confirmed the abundance of protein coating. Thus, our protocol allows effective isolation of SVs from small volumes of mammalian brain tissue, and the properties of the isolated SVs are close to those in vivo, making them suitable for biochemical analysis.

Ultrathin and handleable nanofibrous net as a novel biomimetic basement membrane material for endothelial barrier formation

Many strategies have been adopted to develop porous membranes to reconstitute basement membrane in vitro, which play a key role in the development of in vitro biomimetic models. However, the development of an artificial basement membrane combines cytocompatibility and nano-thickness is still challenging. Herein, a monolayer nanofibrous net patch was fabricated by combining microfabrication and electrospinning as a biomimetic basement membrane material, which was demonstrated for endothelial barrier formation. The nanofibrous net patches with different fiber densities were obtained by controlling electrospinning time. The net was with high porosity and ultrathin thickness approximate to the diameter of nanofibers, which is comparable to that of the native basement membrane. The morphology, proliferation and cell-cell/cell-substrate interactions of endothelial cells on the nanofibrous nets were studied and compared with track-etched polycarbonate membrane and traditional multilayer nanofibers membrane. In addition, the results of TEER measurement and permeability test demonstrated that the endothelial barrier formed on the nanofibrous net patch displayed stronger barrier integrity and function. Therefore, the proposed nanofibrous net patch shows great potential as a novel biomimetic basement membrane, which is promising to be applied for in vitro tissue mimetic applications.

Bioapplications of Magnetic Nanowires: Barcodes, Biocomposites, Heaters.

Magnetic nanowires (MNWs) can have their moments reversed via several mechanisms that are controlled using the composition, length, diameter, and density of nanowires in arrays as-synthesized or as individual nanoparticles in assays or gels. This tailoring of magnetic reversal leads to unique properties that can be used as a signature for reading out the type of MNW for applications as nano-barcodes. When synthesized inside track-etched polycarbonate membranes, the resulting MNW-embedded membranes can be used as biocompatible bandaids for detection without contact or optical sighting. When etched out of the growth template, free-floating MNWs are internalized by cells at 37 °C such that cells and/or exosomes can be collected and detected. In applications of cryopreservation, MNWs can be suspended in cryopreservation agents (CPAs) for injection into the blood vessels of tissues and organs as they are vitrified to -200 °C. Using an alternating magnetic field, the MNWs can then be nanowarmed rapidly to prevent crystallization and uniformly to prevent cracking of specimens, for example, as grafts or transplants. This invited paper is a review of recent progress in the specific bioapplications of MNWs to barcodes, biocomposites, and nanowarmers.