Diffusive flux of nanoparticles through chemically modified alumina membranes

Surface chemistry plays an important role in determining flux through porous media such as in the environment. In this paper diffusive flux of nanoparticles through alkylsilane modified porous alumina is measured as a model for understanding transport in porous media of differing surface chemistries. Experiments are performed as a function of particle size, pore diameter, attached hydrocarbon chain length and chain terminus, and solvent. Particle fluxes are monitored by the change in absorbance of the solution in the receiving side of a diffusion cell. In general, flux increases when the membranes are modified with alkylsilanes compared to untreated membranes, which is attributed to the hydrophobic nature of the porous membranes and differences in wettability. We find that flux decreases, in both hexane and aqueous solutions, when the hydrocarbon chain lining the interior pore wall increases in length. The rate and selectivity of transport across these membranes is related to the partition coefficient (K(p)) and the diffusion coefficient (D) of the permeating species. By conducting experiments as a function of initial particle concentration, we find that K(p)D increases with increasing particle size, is greater in alkylsilane-modified pores, and larger in hexane solution than water. The impact of the alkylsilane terminus (-CH(3), -Br, -NH(2), -COOH) on permeation in water is also examined. In water, the highest K(p)D is observed when the membranes are modified with carboxylic acid terminated silanes and lowest with amine terminated silanes as a result of electrostatic effects during translocation.     

Supported liquid membranes modification with sulphonated poly(ether ether ketone): Permeability,selectivity and stability

The development of a new type of composite membrane consisting of a microfiltration support membrane, an immobilised liquid membrane phase and a hydrophilic, charged polymer layer and its function as a supported liquid membrane (SLM) for copper selective transport are described. The ion-exchange layers function as stabilisation layers to improve the membrane lifetime and consist of sulphonated poly(ether ether ketone) (SPEEK). This polymer shows a high permeability for copper ions due to the presence of fixed negative charges and to its swelling capacity in an aqueous phase.A method was developed to prepare composite membranes composed of the support membranes Celgard with one stabilisation layer on either the feed or strip side of the membrane or on both sides. Good adhesion of homogeneous, negatively charged, hydrophilic SPEEK layers to the hydrophobic macroporous support membranes could only be established when the support membranes were first hydrophilised with a concentrated sulphuric acid solution containing 5 wt% free SO₃.The lifetime of the SLMs is significantly improved when one stabilisation layer is applied at the strip side or two layers at both sides of the SLM. A second advantage of this composite SLM is the increase in copper flux caused by a decrease in thickness of liquid membrane phase. However, when SPEEK penetrates entirely through some pores of the support membrane, ions diffuse non-specifically through the SPEEK matrix resulting in an undesired selectivity loss. This phenomenon occurs only when thin Celgard membranes are used as support membranes.     

Coupled transport membranes II: : The mechanism of uranium transport with a tertiary amine

This paper describes the parameters controlling the coupled transport of uranium anions through liquid membranes. The membranes consist of a microporous polymeric support with a liquid, tertiary amine complexing agent held within the pores by capillary forces. When this liquid membrane is interposed between two aqueous solutions of unequal ion concentrations, the complexing agent can pick up the anion on one side of the membrane and carry it across the membrane by diffusion in the form of a neutral complex. Ions of opposite charge may be carried in the same direction, or ions of like charge may be carried in the opposite direction. We refer to these two modes of transport as “co-transport” and “counter-transport”, respectively. In the coupled transport of uranium, both co-transport and counter-transport can occur. p]The coupling of the flows of two ions permits one of the ions to be pumped against its concentration gradient. We have demonstrated “uphill diffusion” of uranium against substantial concentration gradients, and at significant rates. A number of factors affect uranium flux, principally the concentrations of uranium and the coupled ion in the aqueous solutions. The base strength of the tertiary amine is also an important parameter.     

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.     

High sensitivity binary gas integrity test for membrane filters

A novel non-destructive integrity test for microporous and ultraporous membranes has been developed that is far more sensitive to detecting defects than a conventional gas–liquid diffusion test. The test developed here uses a binary gas mixture and is based on the principle of differing gas permeabilities through the liquid layer of a wetted membrane that results in a concentration enhancement of the faster permeating gas. In an integral membrane, the permeate composition can be predicted based on the transport properties of the gases permeating through the liquid layer and the known operating conditions. A deviation from the expected concentration is an indication of the presence of a defect or open pores. Unlike the gas–liquid diffusion test, the binary gas test has low sensitivity to membrane porosity, liquid layer thickness, and membrane area. Consequently, integral devices will exhibit a relatively narrow range of test values, resulting in a superior defect signal-to-noise ratio. In this study, a binary gas integrity test method was developed and applied to a newly developed virus clearance filter. The binary gas test was demonstrated to provide a significantly higher level of virus retention assurance compared to the air–water diffusion test, and can be implemented by the filter manufacturer as an additional quality assurance test prior to shipping the product to users.     

Interactions and reactions of monolayers and Langmuir-Blodgett multilayers with compounds in the bulk phase

Studies performed on the interactions and reactions of compounds in the bidimensional state, essentially in monolayers and Langmuir-Blodgett multilayers, with substances in the aqueous subphase are reported. More precisely, the following is illustrated: (i) interactions between acid amphiphiles and prevalently bivalent ions placed in the aqueous support and between compounds capable of functioning like ion carriers in monolayers and ions in the subphase, in order to build mimetic membranes capable of selective ion transport; and the complexation of amphiphiles in monolayer with ions in the bulk liquid phase, in order to build chemical sensors to ions; (ii) the reactions of photoinduced electron transfer between a partner in mono- or multimolecular films and a partner in the subphase, which may determine the fundamental parameters and the differences with the same reactions in the bulk phase; and (iii) the reactions of enzymatic hydrolysis between the monolayer of a glyceride, which constitutes the reaction support, and the enzyme in the liquid bulk phase, which constitutes the subphase. The mechanism of the reactions and its inhibition are clarified. To conclude, possible future developments connected with the areas studied are examined.     

PORPHYRIN-LIPID INTERACTIONS AT THE AIR-WATER INTERFACE IN SPREAD MONOLAYERS. A FLUORESCENCE STUDY.

In membrane systems, carboxylic porphyrins may interact with both the lipid pseudophase and the adjacent aqueous environment through their hydrophobic core and their polar acid chains, respectively. These interactions are monitored in model membrane systems, i.e. spread monolayers of dioleoylphosphatidylcholine as functions of lipid organization and pH of the aqueous subphase using steady state and time resolved fluorescence techniques. In all cases contact between porphyrin and aqueous subphase, as indicated through quenching by I^-, is observed at low surface pressure. This contact decreases and becomes almost insignificant as the monolayer approaches maximum organization through compression. On deprotonation of the monocarboxylic porphyrin, methylpyrroporphyrin, increased contact with water is observed in liquid compressed monolayers. In liquid expanded layers, however, it appears that organization of lipid molecules surrounding this dissymmetric charged form affords some isolation from water. The effect of esterification of carboxylic chains is also examined.     

Transport of a liquid water and methanol mixture through carbon nanotubes under a chemical potential gradient

In this work, we report a dual-control-volume grand canonical molecular dynamics simulation study of the transport of a water and methanol mixture under a fixed concentration gradient through nanotubes of various diameters and surface chemistries. Methanol and water are selected as fluid molecules since water represents a strongly polar molecule while methanol is intermediate between nonpolar and strongly polar molecules. Carboxyl acid (-COOH) groups are anchored onto the inner wall of a carbon nanotube to alter the hydrophobic surface into a hydrophilic one. Results show that the transport of the mixture through hydrophilic tubes is faster than through hydrophobic nanotubes although the diffusion of the mixture is slower inside hydrophilic than hydrophobic pores due to a hydrogen network. Thus, the transport of the liquid mixture through the nanotubes is controlled by the pore entrance effect for which hydrogen bonding plays an important role.     

Electromodulated molecular transport in gold-nanotube membranes

We have developed a new class of synthetic membranes that contain monodisperse Au nanotubes with inside diameters of molecular dimensions (<1 nm). The Au nanotubes span the complete thickness of the membrane and can act as conduits for molecule and ion transport between solutions placed on either side of the membrane. We have recently become interested in the concept of electromodulating neutral molecule transport across these membranes. This communication describes a novel approach for accomplishing this objective. This approach makes use of an anionic surfactant which, when a positive potential is applied to the Au nanotube membrane, partitions into the nanotubes to charge the solution side of the electrical double layer at the tube walls. Because of the hydrophobic tail of the surfactant, this renders the nanotube interior hydrophobic, and the membrane now preferentially extracts and transports neutral hydrophobic molecules. Because the anionic surfactant can be expelled from the nanotubes by applying a negative potential, this provides a route for reversibly electromodulating neutral molecule transport in these membranes.     

Water-templated transmembrane nanopores from shape-persistent oligocholate macrocycles

Hydrophobic interactions normally are not considered a major driving force for self-assembling in a hydrophobic environment. When macrocyclic oligocholates were placed within lipid membranes, however, the macrocycles pulled water molecules from the aqueous phase into their hydrophilic internal cavities. These water molecules had strong tendencies to aggregate in a hydrophobic environment and templated the macrocycles to self-assemble into transmembrane nanopores. This counterintuitive hydrophobic effect resulted in some highly unusual transport behavior. Cholesterol normally increases the hydrophobicity of lipid membranes and makes them less permeable to hydrophilic molecules. The permeability of glucose across the oligocholate-containing membranes, however, increased significantly upon the inclusion of cholesterol. Large hydrophilic molecules tend to have difficulty traversing a hydrophobic barrier. The cyclic cholate tetramer, however, was more effective at permeating maltotriose than glucose.     

Coupled transport membranes III: the rate-limiting step in uranium transport with a tertiary amine

This is the second paper describing the coupled transport of uranium ions through liquid membranes. The membranes consist of a microporous polymeric support with an organic solution of a tertiary amine complexing agent held within the pores by capillary forces. p]Both the composition of the organic solution and the structure of the microporous support have a marked effect on uranium flux. With increasing concentration of the agent in an inert diluent, both the amount of uranium that can be extracted into the membrane and the viscosity of the organic solution increase. These opposing effects result in a maximum flux at about 30 vol.% agent in the diluent. The size of the pores in the support also affects the flux; it appears that interaction with the pore walls in membranes with small pores hinders diffusion. p]Two types of interfacial effects have also been observed. The first of these is concentration polarization in the aqueous solution adjacent to the membrane surface. This effect can be reduced by increased stirring. Second, the transmembrane flux of uranium can be limited by the rate of formation (or dissociation) of the uranium complex at the membrane—solution interfaces.     

Interaction between anionic polyelectrolytes and anion exchange membranes and change in membrane properties

Electrodialytic transport properties of anion exchange membranes were measured after formation of anionic polyelectrolyte layers on the membrane surfaces: relative transport number of various anions to chloride ions, current efficiency and apparent diffusion coefficients of neutral molecules. The anionic polyelectrolyte layers were formed by immersing the membrane into an aqueous solution of polycondensation product of sodium naphthalene sulfonate and formaldehyde or polystyrene sulfonic acid.

The change in the relative transport number between anions was remarkable in the anion exchange membrane with high ion exchange capacity by forming the layer. Results were: the relative transport number of sulfate ions to chloride ions decreased and those of nitrate ions to chloride ions, fluoride ions to chloride ions and bromide ions to chloride ions increased compared with the corresponding membrane. Although the apparent diffusion coefficient of neutral molecules suggested clogging of the membrane pores by the polyelectrolyte, anions with higher hydrated ionic diameter were able to permeate through the membrane easily. This means that difference of electrostatic repulsion force against two anions is effective on the change in the relative transport number of anions.     

Compartmentalization and separation of aqueous reagents in the water droplets of water-in-oil high internal phase emulsions

We have compartmentalized aqueous reagents and indicator species within the micrometer-sized water droplets of mixed high internal phase emulsions (HIPEs). Mass transport of the reagents across the micrometer-thickness oil films separating the water droplets followed by reaction with the indicator species produces a visible color change which provides a simple method to measure the trapping times of the reagents. Trapping times have been measured for an uncharged reagent (hydrogen peroxide) and charged reagents (HCl and NaClO) in different HIPEs. The trapping times are discussed in terms of a model in which the transferring species partitions from the water to the oil film followed by a rate-determining step of diffusion across the oil film. Rather surprisingly, it is found that trapping times are of similar orders of magnitude for both uncharged and charged aqueous species transferring across liquid oil films.     

Porous polymer membranes via selectively wetted surfaces

Here, we show that porous polymeric membranes can be prepared using the principles of offset printing: an offset printing plate is structured into hydrophobic and hydrophilic regions with the help of photolithography and is selectively wetted with a solution of calcium chloride in water at the hydrophilic regions. Then, a polymer solution (poly(methyl methacrylate) in chloroform) is applied to this surface and forms a hydrophobic layer that is structured by the aqueous droplets. Deviating from standard offset printing, this layer is not transferred to another surface in its liquid state but is solidified and subsequently is separated from the printing plate. The thickness of the polymer film is chosen in such a way that the aqueous droplets on the surface protrude from the film. Thus, we obtain polymer membranes with pores in the size of the protruding aqueous droplets. These membranes are then characterized by the filtration of model dispersions.     

Thermal effects in osmotic distillation

Osmotic distillation (OD) is a concentration technique for aqueous mixtures based on porous hydrophobic membranes in contact on both sides with liquid phases at pressure lower than the pressure needed to displace the gas phase in the pores. The driving force for the water vapour diffusion through the gas phase immobilised within the membrane pores is sustained by an activity difference by using a hypertonic solution, typically concentrated brines, downstream the membrane. The mass transfer causes a cooling down of the feed and a warm up of the brine, as a consequence a temperature difference is created which reduces the effective driving force for mass transfer. This ‘thermal effect’ is investigated both theoretically and experimentally, it is shown that the effect on the flux is substantial.     

Transport properties and aggregation phenomena of polyoxyethylene sorbitane monooleate (polysorbate 80) in pig gastrointestinal mucin and mucus

The aqueous environment in the gastrointestinal tract frequently requires solubilization of hydrophobic drug molecules in appropriate drug delivery vehicles. An effective uptake/absorption and systemic exposure of a drug molecule entails many processes, one being transport properties of the vehicles through the mucus layer. The mucus layer is a complex mixture of biological molecules. Among them, mucin is responsible of the gel properties of this layer. In this study, we have investigated the diffusion of polyoxyethylene sorbitane monooleate (polysorbate 80), a commonly used nonionic surfactant, in aqueous solution, in mucin solutions at 0.25 and 5 wt %, and in mucus. These measurements were done by using the pulsed field gradient spin echo nuclear magnetic resonance (PGSE-NMR) technique. We conclude that polysorbate 80 is a mixture of non-surface-active molecules that can diffuse freely through all the systems investigated and of surface-active molecules that form micellar structures with transport properties strongly dependent on the environment. Polysorbate 80 micelles do not interact with mucin even though their diffusion is hindered by obstruction of the large mucin molecules. On the other hand, the transport is slowed down in mucus due to interactions with other components such as lipids depots. In the last part of this study, a hydrophobic NMR probe molecule has been included in the systems to mimic a hydrophobic drug molecule. The measurements done in aqueous solution revealed that the probe molecules were transported in a closely similar way as the polysorbate 80 micelles, indicating that they were dissolved in the micellar core. The situation was more complex in mucus. The probe molecules seem to dissolve in the lipid depots at low concentrations of polysorbate 80, which slows down their transport. At increasing concentration of polysorbate 80, the diffusion of the probe molecules increases indicating a continuous dissolution of hexamethyldisilane in the core of polysorbate 80 micelles.     

Modified liquid displacement method for determination of pore size distribution in porous membranes

A new method called constant pressure liquid displacement method (CPLM) was developed and tested to measure the pore size distribution of porous membranes. The permeability, defined as a ratio of the flow rate to the pressure applied, used to be assumed constant either for a conventional liquid displacement method or for a bubble point method, leading to the erroneous interpretation of the pore size distribution. However, it was possible to eliminate such an assumption by measuring the flow rates experimentally at a standard low pressure through the pores penetrated with a permeating liquid according to the proposed method. The pore size distribution for a hydrophobic PVDF membrane was successfully measured by the CPLM and compared with those measured by two different methods such as the conventional liquid displacement method and the mercury intrusion method.     

Retention of volatile organic flavour/fragrance components in the concentration of liquid foods by osmotic distillation

Nine types of hydrophobic microporous membranes were tested for their influence on the retention of a range of volatile organic species when model aqueous solutions of the latter were subjected to osmotic distillation. Similar studies were carried out on Gordo grape juice and Valencia orange juice. Gas chromatography–mass spectrometry head-space analyses of the feed materials coupled with scanning electron microscopy and image analyses of the membranes used indicated that lower organic volatiles flux to water flux ratios occurred when pore sizes at the membrane surface were relatively large. The results have been interpreted in terms of differences in feed-membrane and stripper-membrane boundary layer resistances to organic volatiles transport resulting from different degrees of liquid intrusion into the membrane pores.     

Effect of sucrose on the properties of caffeine adsorption layers at the air/solution interface

Sweet and bitter tastes are known to be mediated by G-protein-coupled receptors. The relationship between the chemical structure of gustable molecules and their molecular organization in saliva (aqueous solution) near the surface of the tongue provides a useful tool for elucidating the mechanism of chemoreception. The interactions between stimulus and membrane receptors occur in an anisotropic system. They might be influenced by the molecular packing of gustable molecules within an aqueous solvent (saliva) close to the receptor protein. To investigate the molecular organization of a sweet molecule (sucrose), a bitter molecule (caffeine), and their mixture in an aqueous phase near a "wall", a hydrophobic phase, we modeled this using an air/liquid interface as an anisotropic system. The experimental (tensiometry and ellipsometry) data unambiguously show that caffeine molecules form an adsorption layer, whereas sucrose induces a desorption layer at the air/water interface. The adsorption of caffeine molecules at the air/water interface gradually increases with the volume concentration and is delayed when sucrose is added to the solution. Spectroscopic ellipsometry data show that caffeine in the adsorption layer has optical properties practically identical to those of the molecule in solution. The results are interpreted in terms of molecular association of caffeine with itself at the interface with and without sucrose in the subphase, using the theory of ideal gases.