Membrane Material Properties Research Articles

Optical Metrology of Adaptive Membrane Mirrors

Current space-based imaging platforms are significantly constrained in both size and weight by the launch vehicle. Increased payload size and weight increases the cost and decreases the selection of launch vehicles. The challenge of membrane optics in space is implementing adaptive optics technology via a membrane surface that provides at least rough order of magnitude imaging—enabling a large lightweight imaging system where small can be eliminated by processes such as real time holography. A system was developed which categorizes surface properties of optical quality membrane material with the ability to interpret membrane mirror deformation. Membrane mirrors with adaptive control were constructed and analyzed using this system which provided sub-micron deformation data with associated optical aberrations, proving the ability of PVDF film to provide adaptive control to regions of interest on membrane mirrors. Remaining technical challenges include bonding methods and eventual multi-layer laminate bonding of the PVDF control surfaces to the membrane.

Membrane porosity and hydrophilic membrane-based dehumidification performance

An experimental study examined the relevance of membrane surface properties to the overall performance of hydrophilic membrane-based dehumidifiers (membrane condensers). Specifically, this study examined a model for the overall mass transfer coefficient derived from surface-science sticking-coefficient arguments, which states that performance is a function of a porosity-weighted average of the surface properties of the bulk membrane material and the surface of the fluid filling the membrane pores. Membranes composed of hydrophilic polyvinylidene fluoride, hydrophilic polyethersulfone, mixed cellulose ester, and 316 stainless steel with porosities between 6 and 80% were used in a flat format for mass transfer measurements in an insulated humid airflow chamber with controlled gas-phase fluid dynamics. While the experiments did not disprove the model, they did not find any meaningful performance differences among the various membrane materials tested, due to membrane surface properties, compared with the gas-side fluid dynamics.

Potentiometric Anion Selective Sensors

In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the transducer element and the aqueous solution, and the receptor molecule that introduces the selectivity. This review deals with potentiometric transduction elements that convert membrane potentials into a signal. The structure and properties of membrane materials is discussed. The nature of the anion receptor ultimately determines the selectivity. Both coordination chemistry and hydrogen bonding have been used to design anion receptor molecules. The integration of all three elements by covalent linkage of all elements in durable sensorsystem concludes the review.

Potentiometric Anion Selective Sensors

In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the transducer element and the aqueous solution, and the receptor molecule that introduces the selectivity. This review deals with potentiometric transduction elements that convert membrane potentials into a signal. The structure and properties of membrane materials is discussed. The nature of the anion receptor ultimately determines the selectivity. Both coordination chemistry and hydrogen bonding have been used to design anion receptor molecules. The integration of all three elements by covalent linkage of all elements in durable sensorsystem concludes the review.

Basis of Permeability/Selectivity Tradeoff Relations in Polymeric Gas Separation Membranes

Gas separation properties of polymer membrane materials follow distinct tradeoff relations: more permeable polymers are generally less selective and vice versa. Robeson1 identified the best combinations of permeability and selectivity for important binary gas pairs (O2/N2, CO2/CH4, H2/N2, etc.) and represented these permeability/selectivity combinations empirically as αA/B = βA/B , where PA and PB are the permeability coefficients of the more permeable and less permeable gases, respectively, αA/B is selectivity (=PA/PB), and λA/B and βA/B are empirical parameters. This report provides a fundamental theory for this observation. In the theory, λA/B depends only on gas size. βA/B depends on λA/B, gas condensability, and one adjustable parameter.

A Finite Element Based Method to Determine the Properties of Planar Soft Tissue

A finite element based method to determine the incremental elastic material properties of planar membranes was developed and evaluated. The method is applicable to tissues that exhibit inhomogeneity, geometric and material nonlinearity, and anisotropy. Markers are placed on the tissue to form a four-node quadrilateral element. The specimen is loaded to an initial reference state, then three incremental loading sets are applied and the nodal displacements recorded. One of these loadings must include shear. These data are used to solve an over-determined system of equations for the tangent stiffness matrix. The method was first verified using analytical data. Next, data obtained from a latex rubber sheet were used to evaluate experimental procedures. Finally, experiments conducted on preconditioned rat skin revealed nonlinear orthotropic behavior. The vector norm comparing the applied and calculated nodal force vectors was used to evaluate the accuracy of the solutions.

Determination of red blood cell shape recovery time constant in a couette system by the analysis of light reflectance and ektacytometry

Red blood cell (RBC) shape change under shear is generally reversible, with the time course of shape recovery a function of the elastic and viscous properties of the RBC membrane. RBC shape recovery can be investigated, using several different techniques, to provide information about the membrane material properties that are not directly accessible by frequently used methods to assess RBC deformability ( e.g., micropore filtration). In the present study, RBC shape recovery was studied in a Couette system after abrupt cessation of shear, either by analyzing the time course of laser light reflection or by serial measurements of elongation indexes from laser diffraction patterns. The time course of shape recovery monitored with both techniques can be described with an exponential equation. Calculated time constants for normal human RBC were 119 ± 17 msec and 97 ± 15 msec as measured by light reflection and ektacytometry, respectively. Treatment of RBC with glutaraldehyde resulted in dose-dependent decreases in the shape recovery time constant. Heat treatment (48 ° C, 20 min), which is known to increase mainly the shear elastic modulus of the membrane, decreased the time constant by 65%. In contrast, wheat germ agglutinin treatment increased the shape recovery time constant by 22%, presumably by increasing membrane surface viscosity. Our results indicate that the shape recovery time constant of RBC can be measured easily and accurately by computerized light reflection analysis.

Influenza-virus-liposome lipid mixing is leaky and largely insensitive to the material properties of the target membrane.

Monolayer intrinsic curvature, void stabilization, and membrane rupture tension have been suggested as important factors determining the rate of membrane fusion. Here, we have studied the kinetics of fusion between influenza virus and target liposomes as a function of various target membrane material properties. In order to examine the fusion process directly, a simple prebinding step is used and proven to be adequate to achieve fusion-rate-limiting kinetics. To test the hypothesis about membrane curvature and void stabilization, we studied the lipid mixing kinetics with dioleoylphosphatidylcholine (DOPC)/ganglioside GD1a (GD1a) liposomes containing lysooleoylphosphatidylcholine (LPC, positive curvature), dioleoyglycerol (DOG, negative curvature), arachidonic acid (AA, negative curvature), and hexadecane (HD, void stabilization). DOG, AA, and HD (at 4 mol%) showed no significant effect on the fusion kinetics, while LPC reversibly inhibited influenza HA mediated fusion only at very high concentrations. Using target liposomes with different membrane rupture tension values, no obvious correlation between membrane rupture tension and the rate of lipid mixing was observed. Moreover, a reported potential antiviral compound, tert-butylhydroquinone (t-b-HQ) (Bodian et al., 1993), showed no significant effect on the kinetics of influenza fusion. Finally leakage of liposome contents was detected during lipid mixing. For encapsulated molecules smaller than 450 MW, the kinetics of leakage is very similar to the kinetics of lipid mixing. In fact, leakage was also detected for encapsulated molecules up to 10 000 MW, suggesting that HA mediated lipid mixing is a very leaky process. Since "nonleaky fusion" has been the foundation of influenza fusion models, our work suggests the need for a major revision in the modeling of this process.

Targeting the development of membranes for gas separation

AbstractThis paper presents the new concept of ‘Targeting’ the properties of new membrane materials. Cost parameters are defined in terms of effective selectivity and cost permeability. These new parameters, obtained from the analysis of membrane plant suppliers' bids, are used in a procedure which determines the optimal degree of separation and recovery. The use of the targeting methods is illustrated here in the development of new membranes for the separation of CO from an H2/CO syngas for the large‐scale manufacture of acetic acid. The targeting approach can be extended to include other gas separation technologies and will aid the development of a generic methodology for the design of gas separation processes.

Comparison of ultrathin x-ray window designs

In order to fabricate entrance windows for soft x-ray detectors, various technologies have been developed. Depending on the x-ray-detector type and the environment in which the windows are used, entrance windows must meet several, often contradictory, requirements: while good pressure tolerance and durability as well as gas tightness require thicker structures, good x-ray transmission can only be achieved with thin membranes. In this paper, the suitability of different window types for various applications is discussed. The applicability discussion is based on the results of tests performed on prototype windows, as well as on calculated and measured x-ray transmission properties. A comparative study of endurance vs transmission properties of some candidate membrane materials is also presented. Test results include pressure tolerance and leakage rates as well as some measurements of radiation damage to the window materials. The window technologies presented include coated polyimide membranes with two different supporting schemes as well as submicrometer beryllium membranes.

Variation of membrane charge of nylon 6 with pH

From the analysis of the membrane potential, the magnitude of the Donnan potential was calculated by using the values of the measured parameters. The Donnan potential is the electric potential at the inner position located just a little off the interface and mainly reflects the electric charge within the membrane. On the other hand, the zeta (ζ) potential is the potential at the slipping plane. The slipping plane is at the outer position just a little off the interface. Therefore, it is possible to obtain more precise information on the distribution of the membrane charge, especially at the interface, by comparing the Donnan potential with the ζ-potential. According to this concept, we compared the Donnan potential with the ζ-potential measured for the nylon 6 membrane at various pH values. As a result, it is pointed out that the nylon 6 membrane dissociates only around the membrane/bulk solution interface but scarcely within the membrane. Within the membrane, the effective membrane charge is determined by selectivety adsorbed ions. This conclusion suggests that the electrochemical properties of membranes are different from those proposed based on the properties of membrane materials in a aqueous solution.

Thalassemia: pathophysiology of red cell changes.

The thalassemias are extremely heterogeneous in terms of their clinical severity, and their underlying pathophysiology relates directly to the extent of accumulation of excess unmatched globin chains: alpha in beta thalassemia and beta in the alpha thalassemias. However, the accumulation of each separate globin chain affects red cell membrane material properties and the state of red cell hydration very differently. These observations presumably account for the varying extent of ineffective erythropoiesis and peripheral blood hemolysis in the major variants of thalassemia. The thalassemias are a worldwide group of inherited disorders of globin-chain synthesis that developed in multiple geographic regions, probably because they provided partial protection against malaria. In normal assembly of adult hemoglobin (HbA-alpha 2 beta 2), alpha and beta globin are synthesized by genes on different chromosomes, whereas heme is synthesized primarily on mitochondria. The synthesis of these chains is very tightly coordinated so that the ratio of alpha globin to beta globin (beta in this case including the beta-like globins delta and gamma) is normally 1 +/- 0.05. Furthermore, specific erythroid proteases are designed to attack and destroy excess alpha or beta globin chains, demonstrating the deleterious impact of the accumulation of excess unmatched globin chains. In beta thalassemia, production of beta globin decreases and excess alpha globin accumulates. In alpha thalassemia, on the other hand, this process occurs in reverse. Perhaps in these disorders more than any others, molecular biologists have documented the deletional and transcriptional events leading to diminished synthesis of specific classes of globin chains.(ABSTRACT TRUNCATED AT 250 WORDS)

Comparison of Ultrathin X-Ray Window Designs

In order to fabricate entrance windows for soft x-ray detectors, various technologies have been developed. Depending on the x-ray-detector type and the environment in which the windows are used, entrance windows must meet several, often contradictory, requirements: while good pressure tolerance and durability as well as gas tightness require thicker structures, good x-ray transmission can only be achieved with thin membranes. In this paper, the suitability of different window types for various applications is discussed. The applicability discussion is based on the results of tests performed on prototype windows, as well as on calculated and measured x-ray transmission properties. A comparative study of endurance vs transmission properties of some candidate membrane materials is also presented. Test results include pressure tolerance and leakage rates as well as some measurements of radiation damage to the window materials. The window technologies presented include coated polyimide membranes with two different supporting schemes as well as submicrometer beryllium membranes.

Physical properties of the x-ray membrane materials

Over the last ten years, the materials most used for x-ray membrane applications have been boron nitride, silicon, silicon nitride, silicon carbide, and diamond. This work presents a review of the macroscopic properties (roughness, biaxial Young’s modulus, optical transmission, fracture strength, and radiation hardness) of these materials. From an examination of the overall criteria, it can be concluded that silicon carbide and diamond continue to be the potential material candidates, even if few properties of diamond membranes have still to be improved. On the other hand, to optimize the physical properties of the membrane material, one has to understand the relationship between the macroscopic characteristics of the membrane and its microstructure. To this aim, we have studied two types of SiC membrane materials, namely, (i) plasma enhanced chemical vapor deposited a-SiC:H and (ii) laser ablation deposited a-SiC. The microstructural characterizations were carried out by means of x-ray diffraction, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and elastic recoil detection analysis techniques. We were thus able to (i) point out the role of C–H and Si–H hydrogenated bonds and Si–C bonds in the stress evolution, from compressive to tensile, (ii) demonstrate the linear dependence of the biaxial Young’s modulus upon the Si–C bond density and (iii) show the effect of dangling bonds on the optical transmission.

Differentiation-associated switches in protein 4.1 expression. Synthesis of multiple structural isoforms during normal human erythropoiesis.

Erythroid differentiation is accompanied by dramatic alterations in morphology and membrane mechanical properties resulting, in large part, from reorganization of the membrane skeletal protein network. The 80-kD protein 4.1 is an important organizational component of this membrane skeleton. Recently, it has been recognized that multiple structural isoforms of 4.1 are encoded by a single gene via alternative pre-mRNA splicing, and that an upstream ATG can be spliced in and used for translation of high molecular weight 4.1. We are exploring the hypothesis that differentiation-associated switches in protein 4.1 structure play an important role in membrane reorganization. To study changes in 4.1 gene expression during normal human differentiation, we analyzed 4.1 protein and mRNA structure at various developmental stages. Using immunofluorescence microscopy, we observed high molecular weight 4.1 isoforms in preproerythroblasts producing punctate, predominantly cytoplasmic staining with a perinuclear area of intense fluorescence, while mature red cells expressed very little high molecular weight 4.1. Isoforms containing an alternatively expressed 102-nucleotide exon near the COOH terminus were abundant in both preproerythroblasts and mature cells but produced a punctate distribution of fluorescence over the entire preproerythroblast and intense membrane-associated fluorescence in the erythrocyte. Characterization of RNA by polymerase chain reaction and nuclease protection assays revealed a differentiation-associated switch in pre-mRNA splicing in the spectrin-actin binding domain. Since this domain plays a critical role in regulating membrane material properties, we speculate that this switch may be crucial to reorganization of the skeletal network during erythropoiesis. We conclude that 4.1 isoforms are differentially expressed and differentially localized during erythropoiesis, and that this isoform family is likely to have diverse functions during terminal differentiation.

Determination of osmotic pressure and fouling resistance and their effects of performance of ultrafiltration membranes

A study was made of the effects of material and geometric properties of ultrafiltration (UF) membranes on flux decline due to concentration-polarization (osmotic pressure) and adsorption (fouling) resistances. UF experiments with solutions of β-lactoglobulin and bovine serum albumin on commercial membranes of poly(vinylpyrrolidone)-coated polycarbonate (PC) and regenerated cellulose (RC) were carried out. A three-state experimental strategy based on an osmotic pressure-adsorption model was used to separately determine the effective hydraulic membrane resistance, osmotic pressure, and fouling resistance. By a normalization procedure, the performance of membranes with varying material and geometric characteristics could be compared and evaluated in terms of the extent of flux reduction individually due to concentration-polarization and fouling. Under all the conditions studied, the total flux reduction for the PC membrane was mainly controlled by the fouling resistance and for the RC membrane by the osmotic pressure build-up due to concentration-polarization. The effect of bulk protein concentration, transmembrane pressure, crossflow velocity, pH, and NaCl concentration on the individual, relative contribution to flux reduction by osmotic pressure and fouling were found to depend on membrane material properties.

Red cell membrane cytoskeleton and the control of membrane properties

~ Introduction material properties of the red cell membrane, in particular its unique stability towards shearing forces and its elasticity with respect to linear defor- mation, result from the interaction of the phospho- lipid bilayer with the membrane cytoskeleton that covers its cytoplasmic surface. When this protein network is extracted or destroyed by proteolysis the membrane spontaneously vesiculates. The path- ways through which the proteins exert their effects

Elastic deformation and failure of lipid bilayer membranes containing cholesterol

Giant bilayer vesicles were reconstituted from several lipids and lipid/cholesterol (CHOL) mixtures: stearolyloleoylphosphatidylcholine (SOPC), bovine sphingomyelin (BSM), diarachidonylphosphatidylcholine (DAPC), SOPC/CHOL, BSM/CHOL, DAPC/CHOL, and extracted red blood cell (RBC) lipids with native cholesterol. Single-walled vesicles were manipulated by micropipette suction and several membrane material properties were determined. The properties measured were the elastic area compressibility modulus K, the critical areal strain alpha c, and the tensile strength tau lys, from which the failure energy or membrane toughness Tf was calculated. The elastic area expansion moduli for these lipid and lipid/cholesterol bilayers ranged from 57 dyn/cm for DAPC to 1,734 dyn/cm for BSM/CHOL. The SOPC/CHOL series and RBC lipids had intermediate values. The results indicated that the presence of cholesterol is the single most influential factor in increasing bilayer cohesion, but only for lipids where both chains are saturated, or mono- or diunsaturated. Multiple unsaturation in both lipid chains inhibits the condensing effect of cholesterol in bilayers. The SOPC/CHOL system was studied in more detail. The area expansion modulus showed a nonlinear increase with increasing cholesterol concentration up to a constant plateau, indicating a saturation limit for cholesterol in the bilayer phase of approximately 55 mol% CHOL. The membrane compressibility was modeled by a property-averaging composite theory involving two bilayer components, namely, uncomplexed lipid and a lipid/cholesterol complex of stoichiometry 1/1.22. The area expansion modulus of this molecular composite membrane was evaluated by a combination of the expansion moduli of each component scaled by their area fractions in the bilayer. Bilayer toughness, which is the energy stored in the bilayer at failure, showed a maximum value at approximately 40 mol% CHOL. This breakdown energy was found to be only a fraction of the available thermal energy, implying that many molecules (approximately 50-100) may be involved in forming the defect structure that leads to failure. The area expansion modulus of extracted RBC lipids with native cholesterol was compared with recent measurements of intact RBC membrane compressibility. The natural membrane was also modeled as a simple composite made up to a compressible lipid/cholesterol matrix containing relatively incompressible transmembrane proteins. It appears that the interaction of incompressible proteins with surrounding lipid confers enhanced compressibility on the composite structure.

Glycophorin C Content of Human Erythrocyte Membrane Is Regulated by Protein 4.1

Human erythrocyte transmembrane sialoglycoprotein, glycophorin C, plays a functionally important role in maintaining erythrocyte shape and regulating membrane material properties, possibly through its interaction with protein 4.1. Moreover, it has previously been shown that membranes deficient in protein 4.1 exhibit decreased content of glycophorin C. To further define the relationship between protein 4.1 and glycophorin C, a series of studies were performed using both protein 4.1- and glycophorin C-deficient erythrocytes. Quantitation by flow cytometry showed that the glycophorin C content of cells totally deficient in protein 4.1 was 9% of normal and that of cells partially deficient in protein 4.1 was 44% of normal. Interestingly, while homozygous glycophorin C-deficient cells had no detectable levels of this sialoglycoprotein, cells from obligate heterozygotes had normal levels. Protein 4.1 content of membranes of these glycophorin C-deficient cells was also normal. These data suggest that glycophorin C may be synthesized in excess by erythroid cells and its membrane content regulated by protein 4.1. To investigate if this regulation is due to association between protein 4.1 and glycophorin C, we examined the retention of glycophorin C in membrane skeletons (Triton shells) prepared from normal membranes, protein 4.1-deficient membranes, and protein 4.1-deficient membranes reconstituted with exogenous protein 4.1. Glycophorin C is retained by Triton shells prepared from normal membranes, whereas Triton shells prepared from protein 4.1-deficient membranes are totally devoid of this sialoglycoprotein. However, reconstitution of protein 4.1-deficient membranes with purified protein 4.1 resulted in retention of glycophorin C with the Triton shells. This finding suggests that protein 4.1 is necessary for association of glycophorin C with the membrane skeleton. Furthermore, these data suggest that through its interaction with glycophorin C, protein 4.1 may play a role in regulating the membrane content of this sialoglycoprotein in mature human erythrocytes.

Glycophorin C content of human erythrocyte membrane is regulated by protein 4.1

Human erythrocyte transmembrane sialoglycoprotein, glycophorin C, plays a functionally important role in maintaining erythrocyte shape and regulating membrane material properties, possibly through its interaction with protein 4.1. Moreover, it has previously been shown that membranes deficient in protein 4.1 exhibit decreased content of glycophorin C. To further define the relationship between protein 4.1 and glycophorin C, a series of studies were performed using both protein 4.1- and glycophorin C-deficient erythrocytes. Quantitation by flow cytometry showed that the glycophorin C content of cells totally deficient in protein 4.1 was 9% of normal and that of cells partially deficient in protein 4.1 was 44% of normal. Interestingly, while homozygous glycophorin C-deficient cells had no detectable levels of this sialoglycoprotein, cells from obligate heterozygotes had normal levels. Protein 4.1 content of membranes of these glycophorin C- deficient cells was also normal. These data suggest that glycophorin C may be synthesized in excess by erythroid cells and its membrane content regulated by protein 4.1. To investigate if this regulation is due to association between protein 4.1 and glycophorin C, we examined the retention of glycophorin C in membrane skeletons (Triton shells) prepared from normal membranes, protein 4.1-deficient membranes, and protein 4.1-deficient membranes reconstituted with exogenous protein 4.1. Glycophorin C is retained by Triton shells prepared from normal membranes, whereas Triton shells prepared from protein 4.1-deficient membranes are totally devoid of this sialoglycoprotein. However, reconstitution of protein 4.1-deficient membranes with purified protein 4.1 resulted in retention of glycophorin C with the Triton shells. This finding suggests that protein 4.1 is necessary for association of glycophorin C with the membrane skeleton. Furthermore, these data suggest that through its interaction with glycophorin C, protein 4.1 may play a role in regulating the membrane content of this sialoglycoprotein in mature human erythrocytes.