Understanding and tuning of polymer surfaces for dialysis applications

Tailoring membrane properties for biomedical applications, e.g., hemodialysis, have been a challenge which material scientists have been addressing for last few decades. The fundamental challenge lies in identifying and controlling the parameters which are responsible for yielding cytocompatibility and hemocompatibility to the material. The present article is an attempt to understand the physical parameters which are responsible for the biological manifestations of a polymer membrane. Two types of dialysis membranes, viz., high performance membrane and high cutoff, have been synthesized. Membrane surfaces were modified via dry and wet annealing, and conditions of annealing were optimized. Subsequently, physical and surface properties of the membranes after annealing were investigated. In‐depth investigation of biological and blood response has been undertaken on the basis of fundamental parameters like polarizability and surface rigidity. Cell adhesion, proliferation, protein adsorption, hemolysis, platelet adhesion, thrombus formation, and complement activation tests were performed on the membranes. It was observed that dry heating increases surface smoothness but in the process develops cracks on membrane surface as well as increases work of adhesion for blood contact. On the other hand, wet heating of membrane surface not only improves biological performance but it is also easy to retrofit with existing spinning technologies for spinning dialysis membranes. In‐house spinning technology was used to synthesize hemodialysis membranes which were annealed at the optimized conditions, and their surfaces were compared with commercial fibers to ascertain the rationale of annealing as a facile method to lend desired surface properties to membranes. Copyright © 2016 John Wiley & Sons, Ltd.     

A comparative study of jet formation in nozzle‐ and nozzle‐less centrifugal spinning systems

Centrifugal spinning, a recently developed approach for ultra‐fine fiber production, has attracted much attention as compared with the electrospinning, due to its high yield, no solution polarity and high‐voltage electrostatic field requirements, etc. In this study, the jet formation process and spinning parameters on jet path are explored and compared in nozzle‐ and nozzle‐less centrifugal spinning systems. For nozzle‐less centrifugal spinning, fingers are formed at the front of thin liquid film due to the theory of Rayleigh–Taylor instability. We find that the lower solution concentration and higher rotational speed favor the formation of thinner and longer fingers. Then, the critical angular velocity and initial jet velocity for nozzle‐/nozzle‐less centrifugal spinning are obtained in accordance with the balance of centrifugal force, viscous force, and surface tension. When jet leaves the spinneret, it will undergo a series of motions including necking and whipping processes, and then, a steady spiral jet path is formed with its radius getting tighter. Finally, we experimentally study the effect of rotational speed and solution concentration on jet path, which shows that the higher rotational speed results in a larger radius of jet path while the solution concentration has little effect on it. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1547–1559     

Structure formation of integral-asymmetric membranes of polystyrene-block-Poly(ethylene oxide)

For the first time the combination of solution casting and solvent–nonsolvent exchange (phase inversion) has been applied to generate asymmetric membranes with highly ordered hexagonally packed cylinders with perpendicular orientation composed of polystyrene-block-poly(ethylene oxide). The influence of parameters like solvent composition and evaporation time on the membrane formation is presented. The development is based on a study of the solution behavior by dynamic light scattering and the precipitation behavior of the cylinder forming diblock copolymer by turbidity measurements from different solvent and nonsolvent systems. The water flux properties, as an important membrane characteristic, show a time dependent behavior, due to swelling of the polyethylene oxide blocks. The morphologies of the membranes are imaged by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Diffusion and phase separation in polymer solution during asymmetric membrane formation

Most of the commercially available polymeric membranes are prepared by the phase inversion process. In this process a thermodynamically stable polymer solution is brought to phase separation by immersing the solution in a surplus of nonsolvent, followed by an exchange of solvent and nonsolvent. The ultimate membrane structure is the result of an interplay of mass transfer and phase separation. Asymmetric membranes as well as symmetrical porous membranes can be obtained. Two types of demixing processes (l-l phase separation and formation of aggregates) can be distinguished by the kinetics of phase separation, as the formation of aggregates is supposed to be a slower process than l-l demixing. Because it is impossible to measure the composition changes during the demixing processes experimentally, a theoretical analysis has to be applied. A suitable formalism to calculate the diffusion induced composition changes in the immersed casting solution, as a function of thermodynamic and hydrodynamic interaction parameters will be described. With this theory it can be shown that two distinctly different mechanisms of membrane formation may occur resulting in two different types of membranes. One type has a relatively thick toplayer and mostly exhibits reverse osmosis, gas separation and pervaporation properties; the other type results in a porous type of membrane, which will exhibit ultra- and microfiltration properties. Model calculations are in agreement with light transmission experiments on membrane forming systems. Therefore, it could be concluded that the elucidation of the diffusion behavior in the immersed polymer film is the key to better understanding of membrane formation by means of immersion precipitation.     

Preparation of asymmetric hollow‐fiber membrane with ultrathin dense skin layer on the outer surface using dry/wet phase inversion process

The authors have developed an asymmetric hollow‐fiber membrane with a skin layer on the outer surface using a dry/wet phase inversion process with a newly synthesized aromatic fluorinated polyamide. Because the skin layer is ultrathin and has no defects, the membrane has gas selectivity in addition to higher gas flux. The membrane has excellent hemocompatibility, which is probably related to packing density of the skin layer. Authors are now clarifying the mechanism of the microstructure formation of the membrane relating to spinning conditions by the standing point of polymer physics. Generally, the microstructure of a polymeric membrane prepared by a phase inversion process is discussed using the phase diagram of the system. However, the process is so dynamic that conventional discussion based on the start and end points is not sufficient, but which path is to be chosen on the phase diagram is more important.     

Peculiarities of the formation of track-etched membranes by the data of atomic force microscopy and X-ray scattering

Atomic force microscopy (AFM) is employed to obtain information on the main stages of the preparation of ultrafiltration track-etched membranes based on poly(ethylene terephthalate) (PET). The surface structure of initial commercial samples of PET films and the same films irradiated with various fluxes of accelerated heavy ions and subsequently treated with alkaline that results in the formation of pores owing to track etching is studied. It is shown that the order of the aforementioned stages of the formation of track-etched membranes with various porosities (from 0.02 to 6%) at a typical pore size of about 50 nm leads only to slight changes in surface structural parameters and does not fundamentally affect the polymer structure formed by spherulites with sizes that are comparable with the pore sizes. In this case, nearly the same content of the crystalline phase in the initial film and track-etched membrane are identified by large-angle X-ray scattering. The picture of X-ray scattering by track-etched membranes at small angles fully corresponds to the scattering on cylindrical pores with a diameter of about 50 nm. The analysis of the set of roughness profiles of the surfaces of initial films and track-etched membranes obtained by the AFM technique makes it possible to determine and introduce—in addition to standard parameters of the surface, the mean value of roughness and its standard deviation the correlation length characterizing the mean distance at which the memory of the roughness value is lost. It is shown that treatments resulting in the formation of track-etched membranes favor an increase in the values of roughness and practically do not affect the mean correlation length, thus supporting the conclusion of the invariance of the main structural parameters of the PET surface.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 248–258.Original Russian Text Copyright © 2005 by Solovieva, Timofeeva, Erina, Vstovsky, Krivandin, Shatalova, Apel, Mchedlishvili, Timashev.     

RETINAL SENSITIZED PHOTODYNAMIC DAMAGE TO LIPOSOMES

Abstract. All trans -retinal has been introduced (2 mol %) into artificial membranes made up of egg lecithin, cholesterol and dicetyl phosphate. Illumination of retinal-enriched liposomes at 365 nm induced photodynamic damages; it triggered the sensitized oxidation of the lipids measured by the appearance of a 233 nm absorption band or by the formation of malonyl dialdehyde. Illumination produced an increase of the membrane fluidity detected with the spin label technique and led also to the lysis of the liposomes as revealed by the release of entrapped chromate ions or by changes in light scattering. Singlet oxygen is involved in these photodynamic effects. The results have been discussed in connection with the light damage phenomena which may afflict the rod outer segment membranes.     

ULTRASTRUCTURAL STUDIES OF THE LIGHT-INDUCED CHLOROPLAST SHRINKAGE*

Both Class I (intact) and Class II (without the outer plastid membrane) chloroplasts of Spinacea oleracea exhibit a shrinkage of the thylakoid volume under conditions which lead to the well known light-induced light scattering increases. In the present report this shrinkage has been measured on micrographs prepared by the freeze-etch technique. In cloroplasts kept in darkness through the freezing or in those treated with DCMU prior to exposure to red light, the thylakoids are in a slightly swollen condition: in plastids exposed to red light and no inhibitor, the thylakoid membranes are closely appressed, giving the thylakoid a shrunken appearance relative to the control. It is further shown that Class I chloroplasts which are actively fixing CO₂ do not give appreciable light scattering changes, but lowering the pH away from the optimum for ATP formation (and CO₂ fixation) or adding the uncoupler quinacrine restores the light-induced scattering increases.     

Membrane-forming properties of gemini lipids possessing aromatic backbone between the hydrocarbon chains and the cationic headgroup

Membrane-forming properties of five new gemini cationic lipids possessing an aromatic backbone between the headgroup and hydrocarbon chains have been presented. These gemini lipids differ by the number of polymethylene units [-(CH(2))(n)-] between the cationic ammonium -[N(+)(CH(3))(2)]- headgroups. The membrane-forming properties of these gemini lipids have been studied in detail by transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), high-sensitivity differential scanning calorimetry (DSC), Paldan fluorescence studies, and UV-vis absorption spectroscopy. The electron micrographs and dynamic light scattering of their aqueous suspensions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the n-value of the spacer. Information on the thermotropic and hydration properties of the resulting vesicles was obtained from differential scanning calorimetry and temperature-dependent Paldan fluorescence studies, respectively. Examination of the thermotropic phase-transition properties of the lipid aggregates revealed interesting features of these lipids, which were found to depend on the length of the spacer chain. Paldan fluorescence studies indicate that the membranes of the gemini lipids are less hydrated as compared to that of the monomeric counterpart in their solid-gel state. In contrast in their fluid, liquid-crystalline phase, the hydration of gemini lipid aggregates was found to depend strongly on the length of the spacer. UV-vis absorption studies suggest an apparent H-type aggregate formation in the gemini lipid membranes in the gel states. In fluid state of the lipid membranes, H-aggregate formation was found to be enhanced depending on the length of the spacer. Such an understanding of the properties upon membrane formation from this new class of gemini lipids will be useful for further development of related gene delivery systems.     

Estimating tissue permeability and other bioelectrical parameters using membrane voltage and short-circuit current

Evaluating the acute toxic effects of drugs or toxins is based mainly on studies which require the use of light microscopy. Recently, the effects of such substances on biological membranes, such as the nasal membrane, has been studied using the traditional Ussing chambers, which make it possible to study the transepithelial flux of drugs across membranes and to measure some bioelectrical parameters. A model is described, with which the changes in the membrane permeability, for sodium, potassium and chlorine, can be calculated directly, based on values obtained from the Ussing chamber system. Also, an experiment is described for evaluating the toxic effects of the cholera toxin B subunit, by measuring these changes in isolated rabbit nasal mucosa.     

Description of non-regular membrane structures: a novel phenomenological approach

A new phenomenological approach to the analysis of complex membrane structures and surfaces and the processing of corresponding experimental data obtained, for example, from the roughness study is presented. The methodology is based on a postulate about the crucial information contained in non-regularities of measured spatial dynamic variables, as well as on the acceptance of a new scaling equation. Accordingly, power spectra and structural functions of different orders are determined by non-regularities of different types resulting from dynamical spikes and jumps of the measured variables. It is also shown that equations for power spectra as well as for structural functions are the same at every spatial–temporal level of the system under consideration. It is demonstrated that multi-parametric invariant relationships characterize a new kind of self-similarity. Appropriate phenomenological parameters are introduced. It is shown that these parameters characterize self-similarity in the rate of loss of correlation links between non-regularities of one type as well as self-similarity in the dynamics of memory loss in the dynamic variable, as the spatial distance from any fixed point increases, for non-regularities of a second type. An algorithm is developed which makes it possible to obtain as many parameters as it is necessary for the characterization of the dynamic state of a system and changes of its state during evolution. Application of this approach to the analysis of surface roughness of a perfluorinated cation-exchange membrane coated with platinum layer is demonstrated.     

Dynamic small-angle x-ray scattering from crystalline polymers

The variation in small-angle x-ray scattering (SAXS) for samples of crystalline polymers subjected to oscillatory strains has been observed employing the 10-m SAXS apparatus with a two-dimensional position-sensitive detector at the National Center for Small-Angle Scattering Research at Oak Ridge National Laboratory. Signal averaging has been carried out in accordance with the π/2-sector technique by gating the detection of scattered intensity in synchronism with the sample strain. In-phase and out-of-phase intensity changes have been observed for a high-density polyethylene at various frequencies (0.05–3.2 Hz) and temperatures (0–70°C). Changes are greatest at small scattering angles. Frequency dependence is greatest at lower temperatures, indicating a time-dependent response of the structural changes leading to scattering at these temperatures. The behavior is not pronounced at elevated temperatures. The similarity of the scattering at both azimuthal angles of 0° and 90° suggests the existence of an additional mechanism, perhaps microvoid formation. To evaluate void contribution, the dynamic invariant function is determined as a function of frequency and temperature. It appears that the microvoid formation lags behind the applied strain. The static and swelling SAXS studies present further evidence of void generation during elongation.     

Characterization of the novel ETFE-based membrane

Recently developed ETFE-SA membrane (sulphonated poly(ethylene-alt-tetrafluoroethylene)) has proved to be chemically stable in the direct methanol fuel cell (DMFC). According to methanol permeability measurements, the MeOH permeability through the ETFE-SA membrane is less than 2% of the corresponding value of the Nafion^® membranes. The characterization of the ETFE-SA membranes is done with sophisticated microscopy techniques. The electrochemical inhomogeneity of the membranes is investigated with the scanning electrochemical microscopy (SECM) by mapping proton distribution across the membrane surface. The atomic force microscopy (AFM) is used, when the surface morphology and morphology changes originating from swelling are investigated, while with the scanning electron microscopy (SEM), the composition and the structure of the membranes can be clarified in detail. The sulphur profile along the membrane cross-section gives information about the distribution of sulphonic acid groups and it is detected with the SEM combined with a energy dispersive X-ray spectrometer. Surface hydrophobicity is investigated by water contact angle (CA) measurement. Many remarkable structural differences between different samples are observed during the measurements, e.g. the surface roughness of the ETFE-SA membrane is much higher, when compared to the Nafion^® membranes. Altogether, the surface properties of the ETFE-SA and the Nafion^® membranes are found to differ significantly from each other and the properties of ETFE-SA vary also as a function of manufacturing parameters.     

Structure and properties of ultra-high modulus polyethylene

The relationship between formation, structure and tensile modulus of ultrahigh modulus polyethylene is explained on the basis of a structural model in which entanglements formed during the deformation process play an important rôle. The results of wide- and small-angle X-ray scattering are interpreted in terms of structural parameters derived from this model.     

Membranolytic activity of bile salts: influence of biological membrane properties and composition

The two main steps of the membranolytic activity of detergents: 1) the partitioning of detergent molecules in the membrane and 2) the solubilisation of the membrane are systematically investigated. The interactions of two bile salt molecules, sodium cholate (NaC) and sodium deoxycholate (NaDC) with biological phospholipid model membranes are considered. The membranolytic activity is analysed as a function of the hydrophobicity of the bile salt, ionic strength, temperature, membrane phase properties, membrane surface charge and composition of the acyl chains of the lipids. The results are derived from calorimetric measurements (ITC, isothermal titration calorimetry). A thermodynamic model is described, taking into consideration electrostatic interactions, which is used for the calculation of the partition coefficient as well as to derive the complete thermodynamic parameters describing the interaction of detergents with biological membranes (change in enthalpy, change in free energy, change in entropy etc). The solubilisation properties are described in a so-called vesicle-to-micelle phase transition diagram. The obtained results are supplemented and confirmed by data obtained from other biophysical techniques (DSC differential scanning calorimetry, DLS dynamic light scattering, SANS small angle neutron scattering).     

Structure and properties of complexes formed by cationic polymers and anionic cholesterol-containing liposomes

The adsorption of the synthetic polycation poly(N-ethyl-4-vinylpyridinium bromide) on the surface of three-component lipid vesicles (liposomes) formed from a mixture of anionic cardiolipin, electroneutral egg lecithin, and nonionic cholesterol is studied via laser microelectropheresis, dynamic light scattering, conductometry, fluorescence spectroscopy, and UV spectroscopy. The incorporation of cholesterol into the liposomal membrane increases its microviscosity; however, the membrane remains liquid-crystalline. Simultaneously, an increase in the fraction of cholesterol causes the formation of defects in liposome membranes during their binding with poly(N-ethyl-4-vinylpyridium bromide) and makes complexation irreversible. The results of this study are of interest for predicting the behavior of polyelectrolytes and biologically active structures formed on their basis on the surface of cells and the reaction of the cellular membrane to the adsorbed polymer.     

Thermally induced transformation of mammalian red blood cells during hyperthermia

The structural and transport characteristics of membranes are mainly determined by the state of the cytoskeleton. The characteristic changes in morphology of human (adult donor and cord) and rat Red Blood Cells (RBC) and of their membrane, induced by hyperthermia (46-51 degrees C) have been analyzed. Two different types of morphological changes have been observed to take place during hyperthermia in all studied RBC groups. We have observed either formation and exfoliation of spiculas from membrane, resulting in the formation of large (4-5 mum) sphere-like cell body and small (0.5-1.5 mum) vesicles or cell fragmentation with formation of large (3-3.5 mum) vesicles. The two distinct phenomena are likely to be determined by the heterogeneity of the RBC population in terms of cell age. There was noted the difference of cord RBC from the donor ones in temperature value of transformation beginning, as well as the character of deformation and vesicle formation, that may testify to their less thermoresistance. The ultrastructure of the membrane, studied with the freeze-fracturing technique, testifies to an irreversible character of membrane changes. The aggregation of intramembrane particles (IMPs) as a continuous network testifies to the strengthening of the interactions between denatured spectrin and bilayer integral components.     

Dynamic behavior of water within a polymer electrolyte fuel cell membrane at low hydration levels

Protonic conduction across the membrane of a polymer electrolyte fuel cell is intimately related to the dynamic behavior of water present within the membrane. To further the understanding of water dynamics in these materials, quasielastic neutron scattering (QENS) has been used to investigate the picosecond dynamic behavior of water within a perfluorosulfonated ionomer (PFSI) membrane under increasing hydration levels from dry to saturation. Evaluation of the elastic incoherent structure factor (EISF) reveals an increase in the characteristic length-scale of confinement as the number of water molecules in the membrane increases, tending to an asymptotic value at saturation. The fraction of elastic incoherent scattering observed at high Q over all hydration levels is well fit by a simple model that assumes a single, nondiffusing hydronium ion per membrane sulfonic acid site. The quasielastic component of the fitted data indicates confined dynamic behavior for scattering vectors less than 0.7 A(-1). As such, the dynamic behavior was interpreted using continuous diffusion confined within a sphere at Q < 0.7 A(-1) and random unconstrained jump diffusion at Q > 0.7 A(-1). As the number of water molecules in the membrane increases, the characteristic residence times obtained from both models is reduced. The increased dynamical frequency is further reflected in the diffusion coefficients predicted by both models. Between low hydration (2 H2O/SO3H) and saturation (16 H2O/SO3H), the continuous spherical diffusion coefficient changes from 0.46 +/- 0.12 to 1.04 +/- 0.12 (10(-5) cm2/s) and jump diffusion indicates an increase from 1.21 +/- 0.03 to 2.14 +/- 0.08 (10(-5) cm2/s). Overall, the dynamic behavior of water has been quantified over different length scale regimes, the results of which may be rationalized on the basis of the formation of water clusters in the hydrophilic domain that expand toward an asymptotic upper limit with increased hydration.     

Preparation of composite hollow fiber membranes: co-extrusion of hydrophilic coatings onto porous hydrophobic support structures

Coating a layer onto a support membrane can serve as a means of surface functionalization of membranes. Frequently, this procedure is a two-step process. In this paper, we describe a concept of membrane preparation in which a coating layer forms in situ onto a support membrane in one step by a co-extrusion process. Our aim is to apply a thin ion exchange layer (sulfonated polyethersulfone, SPES) onto a polysulfone support. The mechanical stability and adhesion of the ion-exchange material to the hydrophobic support membrane (polysulfone) has been studied by a systematic approach of initial proof-of-principle experiments, followed by single layer and double-layer flat sheet casting. Critical parameters quantified by the latter experiments are translated into the co-extrusion spinning process. The composite hollow fiber membrane has low flux as a supported liquid membrane for the copper removal due to the low ion exchange capacity of the SPES. The coating layer of the composite membrane is porous as indicated by gas pair selectivity close to unity. However, our new composite membrane has good nanofiltration properties: it passes mono and bivalent inorganic salts but rejects larger charged organic molecules. The experimental work demonstrates that co-extrusion can be a viable process to continuously prepare surface tailored hollow fiber membranes in a one-step process, even if the support and coating material differ significantly in hydrophilicity.     

制膜液黏度对单皮层PVDF中空纤维膜纺制的影响

以二甲基乙酰胺(DMAc)为溶剂,制备聚偏氟乙烯(PVDF)浓度为15%的制膜液,考察了DMAc同时作为内凝胶浴时膜结构的变化.为保持纺膜过程中的稳定性,分别考察了添加剂LiCl、水以及表面活性剂对制膜液黏度的影响.实验发现添加LiCl可以大大提高制膜液的黏度,而水作为添加剂时对黏度的影响与制膜液本身的浓度有关.在不提高制膜液浓度的基础上,通过提高制膜液黏度克服了膜在纺制过程中的不稳定问题,得到阻力较小的,指状孔贯穿的单外皮层中空纤维膜.