Eval membranes for blood dialysis

Both dry- and wet-process were employed for preparing membrane of ethylene-vinylalcohol copolymer (EVAL) for blood dialysis. Asymmetric and symmetric, dense or porous membranes were prepared by the dry-process. The relationship between the structure of membranes and the experimental variables is explained by using a solubility curve model. This model predicts the membrane structure successfully under various conditions, including the change of temperature of the environment, the solvent system and the temperature of polymer solution. For wet-processes, the casting solutions were coagulated in a precipitation bath (water). Three different structures were obtained: finger type, sponge type and particle-bonded type. The cloud point experiment and the polymer segment motion help to understand and control the membrane structure. Some properties of the EVAL membrane for blood dialysis are shown. It is comparable with or better than the commercialized one. This study may prove useful in determing the controlling parameters for the preparation of membranes from other polymers.     

Formation of composite membranes containing hydrophobic polymer layers by electron-beam sputter deposition

The chemical structure and the contact and morphological properties of composite membranes prepared by electron-beam sputter deposition of a polytetrafluoroethylene layer on the surface of track-etched polypropylene membrane have been studied. It has been found that the application of such layers results in bilayer composite membranes with both the layers having hydrophobic properties. It has been shown that an increase in the thickness of the deposited polytetrafluoroethylene layer leads to development of its roughness, resulting in the formation of a polymer with superhydrophobic properties on the surface of the initial membrane.     

双层类脂膜及其在电化学生物传感器中的应用

详细评述了各种双层类脂膜包括传统的双层类脂膜（ＢＬＭ）、固体载体支撑的自组双层类脂膜（ｓ－ＢＬＭ）、固体载体支撑的混合双层类脂膜（ｅ－ＢＬＭ）的制备方法和特性,比较了其优缺点。介绍了双层类脂膜在电化学生物传感器中的应用,并展望了发展前景。     

Charge mosaic membranes prepared from laminated structures of PVA-based charged layers: 1. Preparation and transport properties of charged mosaic membranes

A charge mosaic (CM) membrane has high permselectivity for electrolytes. While there are many reports of attempts to prepare such membranes, it is difficult to make CM membranes for practical applications. We report the preparation of CM membranes from laminated structures of charged-poly(vinyl alcohol) (PVA) membranes. The membranes were prepared by alternately stacking negatively charged base membranes and positively charged base membranes and by cutting the stack of charged layers. Permeation experiments were performed in a dialysis system consisting of the membrane and mixed solutions of KCl and sucrose. Although the salt flux through the membrane was about 30 times less than that through the charge mosaic membrane Desalton^® (Tosoh Co. Ltd.), which was prepared using microphase separation, the permselectivity for salt of our membrane is more than 30 times higher than that of Desalton^®.     

An ionic polymer bead-supported lipid system

In this paper, we report on the preparation of an ionic polymer bead-supported lipid system several hundred micrometers in diameter. The electrostatic attractive interactions between anionic lipids and cationic polymer beads served as a "molecular glue" to immobilize the lipids on the beads, and then the immobilized lipids prompted the spontaneous formation of lipid bilayer membranes. Confocal fluorescence microscopic techniques revealed that the lipid bilayer membranes were located along the outline of the beads. In addition, the integrity of the lipid bilayer membranes was microscopically confirmed by a low-molecular-weight dye (trypan blue) exclusion test.     

Porous biomimetic membranes: fabrication, properties and future applications

A cell membrane is a flexible lipid bilayer with sophisticated functions which dominate the exchange of material, energy and information between the outside and the inside of the cell. In order to understand and imitate these structures and functions, scientists had already developed a variety of mimic membranes which are alike in form based on lipid bilayer and organic channel-molecules. With the rise of nanotechnology, a large number of synthetic nano-devices are widely used to construct porous biomimetic membranes which are alike in spirit instead of the conventional lipid bilayer membranes. This perspective will first introduce several typical methods to fabricate porous biomimetic membranes, and then discuss the "smart" properties and future applications of these membranes in materials transport, energy transformation and signal transduction aspects.     

Asymmetry of current–voltage characteristics: a bilayer model of a modified ion-exchange membrane

The asymmetry of the current–voltage characteristics of ion-exchange membranes is explained in terms of the model of a bilayer fine porous membrane with constant charge distributions over the thickness of layers. This model has previously been proposed for determining diffusion permeability of membranes. In the case of one uncharged (neutral) layer, a set of two implicit algebraic equations is derived for determining the total current–voltage characteristics (CVC) of a membrane. For the first time, implicit algebraic equations are obtained for calculating the limiting currents at different orientations of an anisotropic membrane in an electrodialysis cell and explicit expressions are derived for determining specific conductivity of the membrane from the slope of the ohmic region of a CVC under the approximation of “excluded coions.” The model may be successfully used for describing the CVCs of perfluorinated MF-4SC sulfonic cation-exchange membranes, the surface layers of which are modified with polyaniline or halloysite.     

Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations

In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.     

Asymmetry of diffusion permeability of bi-layer membranes

To reveal the reason of asymmetry of the diffusion permeability of bi-layer electrodialysis membranes the following problems have been solved using the model of "homogeneous porous membrane": - diffusion of non-electrolyte solutions across a bi-layer membrane; - diffusion of electrolyte solutions across a non-charged bi-layer membrane; - diffusion of electrolyte solutions across a charged single layer membrane; - diffusion of electrolyte solutions across a charged bi-layer membrane. It is shown that the main factor responsible for the asymmetry is the difference between absolute values of densities of fixed charges (or so called "exchange capacities") of different layers of a membrane under investigation. Only in this case the ratio of the thickness of the membrane layers as well as the ratio of ion diffusivities contributes also to the asymmetry of the diffusion permeability. In the present review we survey and generalize our previous investigations and propose a new theory of asymmetry of diffusion permeability of bi-layer membranes. We have deduced explicit algebraic formulas for the degree of asymmetry of diffusion permeability of bi-layer membranes under consideration.     

Effect of dextran polymer on glycocalyx structure and cell electrophoretic mobility

We determined the electrophoretic mobility of human red blood cells suspended in physiological dextran solution for polymer samples with different polydispersity indexes. The electrophoretic mobility of cells is shown to depend mainly on the physical and hydrodynamical characteristics of the porous glycocalyx coating the membrane bilayer. We then propose a new model for the observed increases in effective mobility when cells are exposed to neutral polymers. The extension of glycoproteins under the action of weakly adsorbed chains is shown to reduce the frictional interaction of the surface coat on the flowing liquid. Such a structural rearrangement of the outer membrane improves the penetration of the electro-osmotic flow within the glycocalyx and increases the effective cell mobility.     

Effect of the phase state of the lipid bilayer on the structure and characteristics of the polycation-(anionic liposome) complex

Interaction of the cationic polymer poly-N-ethyl-4-vinylpyridinium bromide with bilayer vesicles (liposomes) composed of zwitterionic dipalmitoylphosphatidylcholine and anionic cardiolipin (the molar fraction of the negatively charged cardiolipin groups is 0.2) is studied. The composition and characteristics of the polycation-liposome complex are shown to be controlled by the phase state of the lipid membrane. Liposomes whose membranes exist in their LC state (“liquid” liposomes) keep their integrity in the complex with polycation. The adsorbed polycation can be completely removed from the liposomal membrane by the addition excess amounts of a competing polyanion. The adsorption of polycation on the surface of liposomes whose membranes exist the gel state (“solid” liposomes) leads to the formation of defects in the membrane, and the polycation’s adsorption with such liposomes becomes irreversible. The defects that form are also preserved when solid liposomes on whose surface the polycation is sorbed are transformed into the liquid state. Moreover, the reversible contact between polycation and liquid liposomes becomes irreversible once the liposomal membranes bound to the polycation transform into the solid state.     

Dewetting-induced membrane formation by adhesion of amphiphile-laden interfaces

We introduce an approach for forming bilayer polymer membranes by adhesion of amphiphile-laden interfaces. This adhesion is induced by a reduction of solvent quality for the amphiphilic diblock copolymers through selective evaporation of good solvent in the solvent mixture. By combining this membrane formation mechanism with a double-emulsion-templated approach for vesicle formation, we fabricate monodisperse polymersomes that exhibit excellent membrane uniformity, and structural stability, using a method that has high encapsulation efficiency. Moreover, we also show that the technique is versatile and can be applied to different block copolymers. The ability to direct the assembly of amphiphiles into a membrane creates new opportunities to engineer the structures of vesicles on the level of the individual bilayer leaflets.     

Biomimetic membranes with aqueous nano channels but without proteins: impedance of impregnated cellulose ester filters

Earlier we have shown that many important properties of ionic aqueous channels in biological membranes can be imitated using simple biomimetic membranes. These membranes are composed of mixed cellulose ester-based filters, impregnated with isopropyl myristate or other esters of fatty acids, and can be used for high-throughput drug screening. If the membrane separates two aqueous solutions, combination of relatively hydrophilic polymer support with immobilized carboxylic groups results in the formation of thin aqueous layers covering inner surface of the pores, while the pore volume is filled by lipid-like substances. Because of these aqueous layers biomimetic membranes even without proteins have a cation/anion ion selectivity and specific (per unit of thickness) electrical properties, which are similar to typical properties of biological membranes. Here we describe frequency-dependent impedance of the isopropyl myristate-impregnated biomimetic membranes in the 4-electrode arrangement and present the results as Bode and Nyquist diagrams. When the membranes are placed in deionized water, it is possible to observe three different dispersion processes in the frequency range 0.1 Hz to 30 kHz. Only one dispersion is observed in 5 mM KH(2)PO(4) solution. It is suggested that these three dispersion features are determined by (a) conductivity in aqueous structures/channels, formed near the internal walls of the filter pores at high frequencies, (b) dielectric properties of the whole membrane at medium frequencies, determined by polymer support, aqueous layers and impregnating oil, and, finally, (c) by the processes in hydrated liquid crystal structures formed in pores by impregnating oil in contact with water at low frequencies.     

Tertiary amine-mediated synthesis of microporous carbon membranes

Microporous carbon membranes were prepared on an -alumina support by a pyrolysis of cationic tertiary amine/anionic polymer composites. The precursor solutions contain a thermosetting resorcinol/formaldehyde (RF) polymer and a cationic tertiary amine. Three types of cationic tertiary amines with different chain lengths were used, such as tetramethlammonium bromide (TMAB), tetrapropylammonium bromide (TPAB) and cetyltrimethylammonium bromide (CTAB). A porous structure was produced by a decomposition of the amine and the resulting pores assisted the further gasification of the RF polymer at high temperature. The carbon/alumina membranes have thin and continuous carbon top layers with a thickness of 1 μm. Gas permeation tests were performed using single gases of CO₂, O₂, N₂, CF₄, n-C₄H₁₀ and i-C₄H₁₀, as well as binary mixtures of CH₄/n-C₄H₁₀ and N₂/CF₄ at different temperatures between 23 and 150 °C. The carbon membrane prepared using TMAB showed separation factors higher than 650 for the CH₄/n-C₄H₁₀ mixtures and higher than 8100 for the N₂/CF₄ mixture. From the permeation of pure gases with different molecular sizes, the pore sizes of the carbon membrane prepared using TMAB, TPAB and CTAB are estimated to be 4.0, 5.0 and larger than 5.5 Å, respectively, indicating that the micropore size of the carbon membranes is controllable by using different amines.     

Swelling, functionalization, and structural changes of the nanoporous layered silicates AMH-3 and MCM-22

Nanoporous layered silicate materials contain 2D-planar sheets of nanoscopic thickness and ordered porous structure. In comparison to porous 3D-framework materials such as zeolites, they have advantages such as significantly increased surface area and decreased diffusion limitations because the layers can potentially be exfoliated or intercalated into polymers to form nanocomposite materials. These properties are particularly interesting for applications as materials for enhancing molecular selectivity and throughput in composite membranes. In this report, the swelling and surface modification chemistry of two attractive nanoporous layered silicate materials, AMH-3 and MCM-22, were studied. We first describe a method, using long-chain diamines instead of monoamines, for swelling of AMH-3 while preserving its pore structure to a greater extent during the swelling process. Then, we describe a stepwise functionalization method for functionalizing the layer surfaces of AMH-3 and MCM-22 via silane condensation reactions. The covalently attached hydrocarbon chain molecules increased the hydrophobicity of AMH-3 and MCM-22 layer surfaces and therefore allow the possibility of effectively dispersing these materials in polymer matrices for thin film/membrane applications.     

Challenges and strategies in the preparation of large‐volume polymer‐based monolithic chromatography adsorbents

To date, the number of published reports on the large‐volume preparation of polymer‐based monolithic chromatography adsorbents is still lacking and is of great importance. Many critical factors need to be considered when manufacturing a large‐volume polymer‐based monolith for chromatographic applications. Structural integrity, validity, and repeatability are thought to be the key factors determining the usability of a large‐volume monolith in a separation process. In this review, we focus on problems and solutions pertaining to heat dissipation, pore size distribution, “wall channel” effect, and mechanical strength in monolith preparation. A template‐based method comprising sacrificial and nonsacrificial techniques is possibly the method of choice due to its precise control over the porous structure. However, additional expensive steps are usually required for the template removal. Other strategies in monolith preparation are also discussed.     

Synthesis and characterization of palladium containing membranes based upon polyacrylic acid

Different methods are described to synthesize a highly porous polymer membrane with fine dispersed metal-nanoparticles. The preparation of the porous catalytic membranes happens by crosslinking of polyacrylic acid dispersions with bifunctional crosslinker in presence of palladium particles. Palladium-nanoparticles, stabilized with the block copolymer polystyrene-block-polyethyleneoxide, can be immobilized in the polymer network in different ways. The polymer/metal network can be prepared in the form of thin flat membranes and dried under retention of the porosity and three-dimensional network structure. Different reduction and preparation methods were applied in order to obtain differences in particle size and distribution of the palladium. The morphology of the material was investigated by scanning electron microscopy. Transmission electron microscopy was employed to show the size and distribution of the metal-nanoparticles in the polymeric matrix. The catalytic activity of the obtained membranes was investigated for the gas phase hydrogenation of cyclohexene and propyne.     

Microscopic behavior of polyvinylpyrrolidone hydrophilizing agents on phase inversion polyethersulfone hollow fiber membranes for hemofiltration

In some biomedical applications, hollow fiber membranes are highly demanded with desirably asymmetric structures, characterized by a dense selective inner skin with which the blood is in contact and supported by porous outer-layer. In this work, such membranes have been successfully prepared by appropriately adjusting membrane manufacturing parameters. Different molecular weights of polyvinylpyrrolidones (PVPs) were used as the hydrophilizing additives for membrane spinning in order to examine their underlying effects on membrane physicochemical properties, morphological structure, solute rejection behavior and hemofiltration performance. Numerous state-of-the-art characterizations on the resultant membranes showed that the hollow fiber membranes spun with the PVP having a molecular weight of 360K as the additive have the most hydrophilic, smooth and highly net negative charged inner surfaces. These membranes also exhibit the best hemofiltration performance in terms of the characteristically least fouling behavior with a normalized flux above 90%, the highest retention of serum albumin for more than 90%, and the best clearance for the simulated β₂-microglobulin toxin in blood waste.     

Structure of Conducting Polymer Films Prepared on the Surface and in the Pores of Poly(ethylene terephthalate) Track Membranes by Template Synthesis

The results of a structural study of conducting polymer coatings deposited onto poly(ethylene terephthalate) (PET) track membranes by template synthesis are reported. The following aspects of the quality of polymer coatings were studied: the ratio between film and granular polymers, the polymer distribution over the surface of track membranes, and the thickness of polymer layers on the opposite sides of track membranes. The fraction of granular polypyrrole (PPy) on the surface and in the pores of a film increased with pore diameter. A decrease in the polymerization temperature decreased the amount of granular PPy on the surface of membranes, whereas the effect of granular PPy on the water permeability of track membranes remained unchanged. A more homogeneous distribution of PPy over the surface of track membranes can be obtained by density equalization of reacting solutions; however, the fraction of granular PPy on the membrane surface increased in this case. It was found that polymer coatings on the two sides of the surface of a membrane template had different thicknesses. Poly(N-methylpyrrole) completely covered only one side of a track membrane facing a monomer solution.     

On the use of gamma irradiation crosslinked PVA membranes in hydrogen fuel cells

There is growing interest in the use of fuel cells (FC) with hydrogen as the main fuel for stationary, mobile, and transportation applications. In the FC concept membranes play increasingly important roles. Polymer electrolyte membrane fuel cells (PEMFCs) are considered as the most promising fuel cell technology for a wide range of applications due to the stable operation, the high energy generation yield and the simplicity of the system.In this work, we develop different types of membranes based on poly(vinyl alcohol) (PVA). PVA is a water-soluble polymer that is used in practical applications because of its easy preparation, excellent chemical resistance, thermal and mechanical properties. Crosslinking of the PVA was performed by gamma irradiation since radiation chemistry is found to be a very effective method for constructing three-dimensional polymeric networks. The samples prepared in this way were then immersed in the alkaline solution over a certain period of time to turn them into conductive membranes. Ionic conductivity of the PVA hydrogels, was then measured as a function of concentration of KOH solutions and temperature. Cyclic voltammetry of these PVA hydrogel electrolytes was performed to determine the width of the electrochemical stability window.We examined these membranes impregnated with saturated 6 M KOH electrolyte as polymer membrane for fuel cells application. Our experiments showed that PEMFCs with PVA and Nafion^® membranes had similar polarization curves, under same conditions. Furthermore, PVA membranes proved to be stable during the real cell tests. This study offers a possibility for more earnest approach to the use of PVA membranes for fuel cell applications.