Developing tardigrade-inspired material: Track membranes functionalized with Dsup protein for cell-free DNA isolation.

When developing functionalized biomaterials, the proteins from extremophilic organisms, in particular unique tardigrade disordered proteins, are of great value. The damage suppressor protein (Dsup), initially discovered in the tardigrade Ramazzottius varieornatus and found to be an efficient DNA protector under oxidative and irradiation stress, has been hypothesized to possess a good potential for the development of the material, which can isolate cell-free DNA. With this in mind, DNA-nonadsorbing polyethylene terephthalate track membranes have been functionalized using the Dsup protein via covalent bonding with glutaraldehyde. The filtration experiments have verified the ability of track membranes with the immobilized Dsup protein to adsorb cell-free DNA, with an accumulation capacity of 70 ± 19 mg m-2. The resulting track membrane-based biomaterial might be used in various devices for filtration and separation of cell-free DNA molecules from biological solutions and environmental samples, and also for their accumulation, storage, and further manipulation.

A thin-film polymer heating element with a continuous silver nanowires network embedded inside.

This study presents a method for fabricating a film-based heating element using a polymer material with an array of intersecting conductive elements embedded within it. Track-etched membranes (TM) with a thickness of 10µm were used as the template, and their pores were filled with metal, forming a three-dimensional grid. Due to the unique manufacturing process of TM, the pores inside intersect with each other, allowing for contacts between individual nanowires (NWs) when filled with metal. Experimental results demonstrated that filling the TM pores with silver allows for heating temperatures up to 78 degrees without deformation or damage to the heating element. The resulting flexible heating element can be utilized in medical devices for heating purposes or as a thermal barrier coating.

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.

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.

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.

Interphase Surface Stability in Liquid-Liquid Membrane Contactors Based on Track-Etched Membranes.

A promising solution for the implementation of extraction processes is liquid-liquid membrane contactors. The transfer of the target component from one immiscible liquid to another is carried out inside membrane pores. For the first time, highly asymmetric track-etched membranes made of polyethylene terephthalate (PET) of the same thickness but with different pore diameters (12.5-19 nm on one side and hundreds of nanometers on the other side) were studied in the liquid-liquid membrane contactor. For analysis of the liquid-liquid interface stability, two systems widely diverging in the interfacial tension value were used: water-pentanol and water-hexadecane. The interface stability was investigated depending on the following process parameters: the porous structure, the location of the asymmetric membrane in the contactor, the velocities of liquids, and the pressure drop between them. It was shown that the stability of the interface increases with decreasing pore size. Furthermore, it is preferable to supply the aqueous phase from the side of the asymmetric membrane with the larger pore size. The asymmetry of the porous structure of the membrane makes it possible to increase the range of pressure drop values between the phases by at least two times (from 5 to 10 kPa), which does not lead to mutual dispersion of the liquids. The liquid-liquid contactor based on the asymmetric track-etched membranes allows for the extraction of impurities from the organic phase into the aqueous phase by using a 1% solution of acetone in hexadecane as an example.

Osmotic Effects in Track-Etched Nanopores.

Asymmetrically etched ion-track membranes attract great interest for both fundamental and technical reasons because of a large variety of applications. So far, conductometric measurements during track etching provide only limited information about the complicated asymmetric etching process. In this paper, monitoring of osmotic phenomena is used to elucidate the initial phase of nanopore formation. It is shown that strong alkaline solutions generate a considerable osmotic flow of water through newborn conical pores. The interplay between diffusion and convection in the pore channel results in a substantially nonlinear alkali concentration gradient and a rapid change in the pore geometry after breakthrough. Similar phenomena are observed in experiments with cylindrical track-etched pores of 15-30 nm in radius. A theoretical description of the diffusion-convection processes in the pores is provided.

Ultrafast ion sieving using nanoporous polymeric membranes.

The great potential of nanoporous membranes for water filtration and chemical separation has been challenged by the trade-off between selectivity and permeability. Here we report on nanoporous polymer membranes with an excellent balance between selectivity and permeability of ions. Our membranes are fabricated by irradiating 2-µm-thick polyethylene terephthalate Lumirror® films with GeV heavy ions followed by ultraviolet exposure. These membranes show a high transport rate of K+ ions of up to 14 mol h-1 m-2 and a selectivity of alkali metal ions over heavy metal ions of >500. Combining transport experiments and molecular dynamics simulations with a polymeric nanopore model, we demonstrate that the high permeability is attributable to the presence of nanopores with a radius of ~0.5 nm and a density of up to 5 × 1010 cm-2, and the selectivity is ascribed to the interaction between the partially dehydrated ions and the negatively charged nanopore wall.

Shedding light on the mechanism of asymmetric track etching: an interplay between latent track structure, etchant diffusion and osmotic flow.

The method of producing single track-etched conical nanopores has received considerable attention and found many applications in diverse fields such as biosensing, nanofluidics, information processing and others. The performance of an asymmetric nanopore is largely determined by its geometry, especially by the size and shape of its tip. In this paper we reconstruct the profiles of so-called conical pores fabricated by asymmetric chemical etching of ion tracks in polymer foil. Conductometric measurements during etching and field emission scanning electron microscopy examinations of the resulting pores were employed in order to determine the pore geometry. We demonstrate that the pore constriction geometry evolves through a variety of configurations with advancing time after breakthrough. While immediately after breakthrough the pore tips are trumpet-shaped, further etching is strongly affected by osmotic effects which eventually lead to bullet-shaped pore tips. We evidence that the osmotic flow appearing during asymmetric track etching has a determinative effect on pore formation. A convection-diffusion model is presented that semi-quantitatively explains the effect of osmotic processes under asymmetric track etching conditions. In addition, a phenomenon of reagent contaminant precipitation in nanopores is reported and discussed.

Accurate characterization of single track-etched, conical nanopores.

Single track-etched conical nanopores in polymer foils have attracted considerable attention in recent years due to their potential applications in biosensing, nanofluidics, information processing, and other fields. The performance of a nanopore critically depends on the size and shape of its narrowest, nanometer-sized region. In this paper, we reconstructed the profiles of both doubly-conical and conical pores, using an algorithm based on conductometric measurements performed in the course of etching, coupled with SEM data. We showed that pore constriction deviates from the conical shape, and the deviation depends on the energy loss of the particle that produced the track. Funnel-like profiles of tracks of four ions with different atomic numbers were derived from experimental data. The simulations, using a Poisson-Nernst-Planck model, demonstrated that the ion current rectification properties of the funnel-shaped asymmetrical pores significantly differ from those of conical ones if the tip radius of the pore is smaller than 10 nm. Upon subjecting to further etching, the pores gradually approach the "ideal" conical geometry, and the ion transport properties of these two pore configurations become almost indistinguishable.

Asymmetric ion track nanopores for sensor technology. Reconstruction of pore profile from conductometric measurements.

We reconstruct the profile of asymmetric ion track nanopores from an algorithm developed for conductometric measurements of symmetric nanopores. The validity of the reconstruction is supported by FESEM observations. Our analysis reveals that asymmetric pores fabricated by one-sided etching are funnel-like and not conical. The analysis provides the constriction diameter and the pore profile as a function of etching time. The reconstruction of the pore profile defines the starting conditions of asymmetric nanopores at breakthrough. The deviation from the conical shape is most pronounced at the pore tip. This critical zone dominates transport properties relevant to ion conductance, selectivity, current rectification, resistive pulse sensing and biosensors. The classical cone approximation used until now underestimates the tip diameter by a factor of two. As transport processes in nanopores depend in a highly nonlinear way on the constriction diameter the presented reconstruction must be taken into account when studying ionic and molecular transport processes in asymmetric pores.

Effect of nanopore geometry on ion current rectification.

We present the results of systematic studies of ion current rectification performed on artificial asymmetric nanopores with different geometries and dimensions. The nanopores are fabricated by the ion track etching method using surfactant-doped alkaline solutions. By varying the alkali concentration in the etchant and the etching time, control over the pore profile and dimensions is achieved. The pore geometry is characterized in detail using field-emission scanning electron microscopy. The dependence of the ion current rectification ratio on the pore length, tip diameter, and the degree of pore taper is analysed. The experimental data are compared to the calculations based on the Poisson-Nernst-Planck equations. A strong effect of the tip geometry on the diode-like behaviour is confirmed.

Versatile ultrathin nanoporous silicon nitride membranes.

Single- and multiple-nanopore membranes are both highly interesting for biosensing and separation processes, as well as their ability to mimic biological membranes. The density of pores, their shape, and their surface chemistry are the key factors that determine membrane transport and separation capabilities. Here, we report silicon nitride (SiN) membranes with fully controlled porosity, pore geometry, and pore surface chemistry. An ultrathin freestanding SiN platform is described with conical or double-conical nanopores of diameters as small as several nanometers, prepared by the track-etching technique. This technique allows the membrane porosity to be tuned from one to billions of pores per square centimeter. We demonstrate the separation capabilities of these membranes by discrimination of dye and protein molecules based on their charge and size. This separation process is based on an electrostatic mechanism and operates in physiological electrolyte conditions. As we have also shown, the separation capabilities can be tuned by chemically modifying the pore walls. Compared with typical membranes with cylindrical pores, the conical and double-conical pores reported here allow for higher fluxes, a critical advantage in separation applications. In addition, the conical pore shape results in a shorter effective length, which gives advantages for single biomolecule detection applications such as nanopore-based DNA analysis.

Ultrasound attenuation in cylindrical micro-pores: nondestructive porometry of ion-track membranes.

The propagation of ultrasonic waves in the cylindrical micro-pores (pore diam. 1 microm) of ion-track membranes (ITMs) is studied. This membrane fabrication technique provides unique possibilities to obtain cylindrical micro-pores with a very high degree of accuracy in pore shape, size, and orientation. Several ITMs were specially produced having the same pore diameter, orientation, and geometry, but different thickness. Porosity, pore diameter, and shape were determined using scanning electron microscopy, and then the coefficient of ultrasound transmission was measured using air coupling and spectral analysis. These experimental conditions permit us to eliminate the influence of the boundary conditions and to achieve a strong decoupling between the fluid filling the pores and the solid constituent of the membrane. Hence, the velocity and the attenuation coefficient for ultrasound propagation in the pores can be measured. These parameters are compared with the predictions made by conventional theories for sound propagation in porous media and in cylindrical channels. The conclusions of this work provide a better understanding of wave propagation in micro-pores and establish the basis of an ultrasonic porometry technique for ITMs.

Synthetic nanopores as a test case for ion channel theories: the anomalous mole fraction effect without single filing.

The predictions of a theory for the anomalous mole fraction effect (AMFE) are tested experimentally with synthetic nanopores in plastic. The negatively charged synthetic nanopores under consideration are highly cation selective and 50 A in diameter at their smallest point. These pores exhibit an AMFE in mixtures of Ca(2+) and monovalent cations. An AMFE occurs when the conductance through a pore is lower in a mixture of salts than in the pure salts at the same concentration. For ion channels, the textbook interpretation of the AMFE is that multiple ions move through the pore in coordinated, single-file motion. However, because the synthetic nanopores are so wide, their AMFE shows that single filing is not necessary for the AMFE. It is shown that the AMFE in the synthetic nanopores is explained by a theory of preferential ion selectivity. The unique properties of the synthetic nanopores allow us to experimentally confirm several predictions of this theory. These same properties make synthetic nanopores an interesting new platform to test theories of ion channel permeation and selectivity in general.

Pore structure and function of synthetic nanopores with fixed charges: tip shape and rectification properties.

We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst-Planck equations. According to our results, the nanopore transport properties, such as current-voltage (I-V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.