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.     

Monte Carlo simulation of electrolytes in the constant voltage ensemble

The authors studied the structural, electrostatic, and electromechanical properties of the terlamellar structure composed of the anode, the cathode, and the electrolyte layer separating them. They used the Monte Carlo simulation technique in the constant voltage ensemble, where the electrical potential difference between the anode and the cathode is introduced as an external field. For ions, they used the primitive models of different sizes and valences in order to investigate how they affect the physical properties when an electrical field is applied between the electrodes. For electrodes, they used impermeable and permeable models, which mimic planar and porous electrodes, respectively. The asymmetry between the anions and the cations in size or valence was found to be responsible for the asymmetry in the concentration profile, the potential drop, and the stress distribution, in comparing the anode and the cathode sides. The charging/discharging process in the planar and porous electrodes is discussed at molecular level.     

pH dependence of hydrochloric acid diffusion through gastric mucus: correlation with diffusion through a water layer using a membrane-mounted glass pH electrode

Solute diffusion coefficients (D) can indicate a dependence upon actual solute concentrations. Here a single compartment has been utilized, in which effective HCl diffusion to a membrane-mounted glass pH electrode can be measured across the pH spectrum. The study has investigated HCl diffusion through both mucus and water layers as a function of HCl concentration. The observed dynamic responses of a liquid-film and mucus-coated electrodes over a range of HCl concentrations suggest that the speed at which equilibrium is attained is pH dependent; equilibrium was reached rapidly under more acidic and alkaline conditions. Estimated values of DHCl also indicate a strong pH dependence for both liquid film and mucus. In both instances, a greater than 10-fold reduction in DHCl at pH 7.5 as compared with that at pH 3.5 has been demonstrated. Furthermore, estimated values of DHCl are approximately 4-fold smaller through the mucus gel, as compared with a water layer. The findings indicate that the most powerful influence on diffusional resistance is pH itself, whereby a marked drop in H+ diffusion is likely to occur towards neutral pH irrespective of the composition of the gel barrier. Possible implications of the findings are discussed in relation to mucosal protection from acid.     

Electrokinetics of diffuse soft interfaces. 2. Analysis based on the nonlinear Poisson-Boltzmann equation

In a previous study (Langmuir 2004, 20, 10324), the electrokinetic properties of diffuse soft layers were theoretically investigated within the framework of the Debye-Hückel approximation valid in the limit of sufficiently low values for the Donnan potential. In the current paper, the electrokinetics is tackled on the basis of the rigorous nonlinearized Poisson-Boltzmann equation, the numerical evaluation of the electroosmotic velocity profile, and the analytically derived hydrodynamic velocity profile. The results are illustrated and discussed for a diffuse soft interface characterized by a linear gradient for the friction coefficient and the density of hydrodynamically immobile ionogenic groups in the transition region separating the bulk soft layer and the bulk electrolyte solution. In particular, it is shown how the strong asymmetry for the potential distribution, as met for high values of the bulk fixed charge density and/or low electrolyte concentrations, is reflected in the electrokinetic features of the diffuse soft layer. The analysis clearly highlights the shortcomings of the discontinuous approximation by Ohshima and others for the modeling of the friction and electrostatic properties of soft layers exhibiting high Donnan potentials. This is in line with reported electrokinetic measurements of various soft particles and permeable gels at low electrolyte concentrations which fail to match predictions based on Ohshima's theory.     

The modern understanding of the glass electrode response

Electrochemical experiments in combination with infrared spectroscopy and subsurface concentration profiling yielded information on ionic processes at the membrane surface of glass electrodes and resulted in a detailed mechanism of the glass electrode response. This dissociation mechanism is based on phase boundary equilibria between anionic groups at the glass surface and hydrogen or alkali ions in the solution, which control the potential of the glass and the concentrations of ions attached to the surface groups. The resulting concentration gradients between glass surface and bulk glass cause an interdiffusion of the different ions, if they are not hindered sterically to penetrate into the glass, and a diffusion potential beneath the glass surface. The interdiffusion determines the course of the glass corrosion, which thus depends on whether protons or alkali ions are attached to the surface and interdiffuse with the alkali ions of the glass, leading, respectively, to a steady-state leached layer or a continuously growing alkali-exchanged layer. pH electrodes with La₂O₃-containing membrane glasses show delayed interfering potential drifts in neutral and alkali phosphate and fluoride solutions caused by LaPO₄ and LaF₃ deposits, respectively, at the membrane surface (phosphate and fluoride errors). Equations for the phase boundary potential and phase boundary concentrations are derived on a thermodynamic and kinetic basis and are verified experimentally. Glass leaching and alkali ion interdiffusion are studied, and the diffusion potential within a leached layer is determined. The formation periods of pH and of pM glass electrodes are explained, and an indirect part of the sodium error and an irreversible sodium error are detected. Leached and alkali-exchanged layers consist of modified glass and are not gel layers as generally assumed. Large exchange current densities of the phase boundary equilibria explain the stability of glass electrode potentials. Migration experiments with subsequent concentration profiling showed that glasses can be alkali ion, proton, and mixed alkali ion-proton conductors and yielded concentration-dependent mobilities of lithium ions and replacing protons in a lithium silicate glass. The unchanged pH response of membranes before and after field-driven protonation, in alkali-free solutions, excludes the exchange of different ions as the origin of the glass electrode response, as assumed by the ion exchange theory, and verifies the dissociation mechanism.     

Temperature Sensitive Hydrogels Based on Hydroxypropylcellulose by High Energy Irradiation

Summary: Stimuli sensitive hydrogels change their properties in dependence on a liquid environment. The temperature sensitive hydroxypropylcellulose (HPC) gel shows a volume phase transition in water at about 48 °C. For different applications a crosslinking of a preformed layer of the dry polymer on a support is necessary. It is known, that HPC dissolved in water is crosslinkable by high energy irradiation (electron beam). Now, we could show, that HPC can be crosslinked in the dry state by high energy irradiation. This allows the preparation of thin crosslinked layers of HPC on silicone substrates.     

Dielectric spectroscopy and calorimetry in the glass transition region of semi-crystalline poly(ethylene terephthalate)

Confinement of the glass-forming regions in the nanometer range influences the α-relaxation which is associated with the glass transition. These effects were investigated for semicrystalline poly(ethylene terephthalate) by dielectric spectroscopy and differential scanning calorimetry. The results are discussed within the concept of cooperative length, i.e. the characteristic length of the cooperative process of glass transition. Both experiments showed a dependence of the glass transition on the mean thickness of the amorphous layers. For the dielectric relaxation, the loss maximum was found to shift to higher temperatures with decreasing thickness of the amorphous layers, but no differences were observed in the curve shape for the differently crystallized samples. For the calorimetric measurements, in contrast, there was no correlation for the glass transition temperature, whereas the curve shape did correlate with the layer thickness of the mobile amorphous fraction. From the structure parameters, a characteristic length of approximately (2.5±1) nm was estimated for the unconfined glass relaxation (transition).     

Reverse Phase Thin-Layer Chromato-Graphy of some Metal Ions on Butyl-Amine Impregnated Silica Gel G in Formic Acid Medium

Abstract

Reversed phase thin layer chromatography of metal ions have been performed on s-butylamine and t-butylamine impregnated silica gel thin layers in formic acid and sodium formate systems. Separation potential of impregnated silica gel thin layers was explored. Impregnated silica gel layers were found to be more selective (strongly sorbing) than unimpregnated silica gel chromo-toplates. Several important binary and ternary separations were achieved on impregnated thin layers.     

Chemical composition and structure of the surface layers-products of interaction between steel 3 and hostile aqueous environment: The effect of the environment

The composition and structure of layers formed by corrosion products at the open-circuit and passive potentials on the surface of steel 3 in aqueous media containing sulfate ions, borate ions, or their mixtures are studied by X-ray photoelectron spectroscopy and secondary ion mass spectrometry. The composition and structure of both the phase surface layers and the adsorption surface layers are found to depend on the solution nature. The composition and structure of a corrosion product layer; the composition of the double layer, in particular, the surface charge and potential; and the anion role as a corrosion inhibitor or activator depend on the way the anion coordinates with the corroding-metal surface. The coordination may be strong, in an inner coordination sphere (borate ions), or less strong, in an outer coordination sphere (sulfate ions) of a cation on the surface.     

Quartz crystal microbalance electrode modified with thermoresponsive crosslinked and non-crosslinked <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide polymers. Response to changes in temperature

Electrochemical quartz crystal microbalance (EQCM) electrode was modified with environmentally sensitive polymers. The polymer layers on the electrode were composed of either crosslinked or non-crosslinked thermoresponsive poly(N-isopropylacrylamide). For anchoring thin gel films on the electrode surface, the electrochemically induced free radical polymerization (EIFRP) was employed. The electroreduction of the peroxydisulfate anion led to generation of free radical. This radical initiated the free radical polymerization process that led to the formation of a thin gel layer attached to the electrode surface. To monitor in situ the growth of the polymer film the changes in resonant frequency of the quartz crystal were recorded. A significant decrease in the frequency (growth of the layer) was seen in the potential range where the reduction of peroxydisulfate anion took place. The morphology of the layers was examined with a scanning electron microscopy (SEM). The phenomenon of volume phase transition (shrinking/swelling process) in the gel layers initiated by a change in temperature was investigated. Unexpected big, sharp, and of negative sign minima appeared at the change-in-frequency vs. temperature plots. These minima were not seen in the plots obtained for the polymers without linker. That situation should be useful in the investigation of chemical interactions proceeding under the conditions of volume phase transition. The influence of volume phase transition on the transport of a member of a model red-ox system, ferro- and ferricyanide couple, and therefore on height of its voltammetric response was examined. The changes in electrochemical properties of the layers induced by volume phase transition were monitored with electrochemical impedance spectroscopy.     

Stationary phases for thin-layer chromatography

This paper presents a review of the literature concerning development of the stationary phases for thin-layer chromatography (TLC) in the last ten years. The silica gel remains the most important adsorbent for TLC separation. The kinetic properties of the silica-gel thin layer and the new TLC plates have been presented. Other materials used as stationary phase were alumina, zirconium oxide, Florisil, and ion-exchanger. Chemically new bonded stationary phase development is also discussed. The improvement of the separations of some organic mixtures by impregnation of silica gel, cellulose, or polyamide plates (with transition metal ions and silver salts) and their applications is presented. The impregnation of the thin layer with organic stationary phase and inclusion complexes is another method used for the enhancement of the separation efficiences. Another modality to improve the selectivity in TLC using ion-pairing as reagent of impregnation is described as well. The actual state of chiral separation by TLC is discussed with concrete references to recent advances in chiral stationary phases. The use of nonpolar chemically bonded stationary phases impregnated with transitional metal ions is presented as chiral stationary phases. The cellulose, modified cellulose, chitin, chitosan, and their derivatives are presented and their potential for the analysis of the racemates is discussed. The cyclodextrines and macrocyclic antibiotics were used with very good results for enantiomeric separation by TLC. A new separation approach with molecular imprinting polymers was reported as a chiral stationary phase in TLC. The examples provide a wide range of structural types that can be readily resolved enantiomerically by TLC.     

Ion exchange properties of monolithic and particle type iminodiacetic acid modified silica

A 10 cm silica monolith has been modified with iminodiacetic acid (IDA) groups and characterised for its selectivity toward alkali, alkaline earth, and selected transition metal cations. Physical characterisation of the modified monolith found non-homogeneous modification along the length of the monolith, although sufficient capacity was achieved to facilitate significant retention of alkaline earth and transition/heavy metal ions over a range of eluent pH and ionic strength conditions. For alkaline earth and transition/heavy metal ions, selectivity of the 10 cm IDA monolith closely matched that seen with a 25 cm IDA modified silica gel particle packed column, although the separation of alkali metal ions was noticeably poorer on the monolithic column. Peak efficiencies for most metal ions were of a similar order for both column types, except for Zn(II), which showed significant peak broadening on the IDA monolithic column.     

New Inexpensive and Selective Sorbent Phases for Rapid Thin Layer Chromatographic Analysis of Metal Ions

Abstract

New sorbent phases have been developed by impregnating silica gel G with different inorganic salts for the analysis of metal ions by thin layer chroma to graphy in carboxylic acids media. Thin layers prepared from silica gel G impregnated with ammonium chloride or barium nitrate show the unusual selectivity towards metal ions in comparison to the thin layers prepared from plain silica gel G or silica gel impregnated with silver nitrate or aluminium nitrate. Many qualitative separations     

Electric field transport of biphilic ions and anchoring transitions in nematic liquid crystals

Anchoring interaction of MBBA and MBBA + 5CB nematic layers with monomolecular films of CTAB on ITO glass supports is studied by videomicroscopy in the presence of an electric field. Planar-planar or homeotropichomeotropic electrode substrates are used to make the nematic cells. The substrate symmetry is broken by coating only one electrode with self-assembled CTAB film. In a DC electric field we observe some new effects; (i) polarity-dependent breaking of anchoring and switching to two oblique states in dielectrically stable planar cells; (ii) a polarity-dependent flow-induced metastable anchoring transition in homeotropic cells to a planar or tilted alignment after the field is switched off. These results are discussed in terms of a surface transition assisted by electric transport of biphilic CTAB ions and by a surface memorization of the flow-induced planar alignment.     

Bulk conductivity of soft surface layers: experimental measurement and electrokinetic implications

Conductivity measurements were carried out on a family of polyacrylamide-co-sodium acrylate gels cross-linked with N,N'-methylenebisacrylamide in a homemade electrokinetic cell. The conductivity data allowed the equilibrium Donnan potential difference between the bulk gel and the bulk electrolyte solution to be estimated at various ionic strengths. The data were fit to a simple model assuming full dissociation of functional groups as well as to a more complete model (Dukhin, S. S.; Zimmerman, R.; Werner, C. J. Colloid Interface Sci. 2004, 274, 309) that accounts for the weak electrolyte nature of the acrylate groups fixed within the gel structure. The conductivity of the gel layers was observed to be significantly larger than the conductivity of the bulk electrolyte solutions at low ionic strengths. The increased conductivity reflects the enhanced concentration of ions within the gel structure due to Donnan equilibrium and the mobility of ions within the high water content gel layers. The electrokinetic implications of the bulk conductivity of gel-like soft surface layers are discussed in terms of the influence of the gel conductance on the resulting streaming potential.     

Studies of host-guest thin films of corona-poled betaine-type polar molecules by kelvin probe technique and atomic force microscopy

In this work betaine-type molecules were investigated. As a result of the asymmetry of charge distribution, molecules possess in the ground state a considerable permanent dipole moment. The decay of surface potential of poled polymer films is dependent at least on two relaxation processes. The influence of glass transition of PMMA on thermal dependence of the surface potential is shown. The transition temperature, where no changes of the surface potential appeared, is related to glass transition temperature of the host-guest system. The topography of the film surface was obtained by AFM.     

Diantipyrilmethane as complex-forming reagents in the thin-layer chromatographic determination of metals

Summary The efficiency of diantipyrilmethane used as a reagent for the chromatographic separation of metals, including titanium, zirconium and hafnium, rare earth elements, transition and platinum metals is shown. The peculiarities of the chromatographic behaviour of metal diantipyrilmethanates and the mechanism of their retention in TLC are discussed. Methods were developed for the determination of metals based on complex formation directly in the sorbent layer or by liquid extraction. The chromatographic separation takes place in silica gel thin layers with elution by organic solvent-mineral acid mixtures. The metals are determined by densitometric or spectrophotometric methods. After the complexes are isolated from the layer. The procedures are characterized by simplicity, efficiency, and a rather high selectivity. They were used to analyze steels, alloys, industrial solutions and other samples.     

Drying and sintering of sol-gel derived large SiO2 monoliths

This review article summarizes the development of drying and sintering techniques for the production of sol-gel derived, large silica glass components. Gels may be synthesized using particulate or metal alkoxide precursors, or both in combination. Rapid fracture-free drying has been achieved easily with particulate gels because of their large pore size (100–6000 Å). Alkoxide gels, which generally have small pores (<200 Å), were initially difficult to dry without cracking. However, recent studies have shown that large alkoxide gel monoliths can also be dried in reasonably short times (<10 days). During subsequent heat treatment, alkoxide gels tend to have high shrinkage rates, which may cause trapping of hydroxyl ions or organic groups remaining on the gel surface. Although the removal of these species is easier for particulate gels, their large pore size necessitates heating above 1400°C to achieve full consolidation. Sintering at such temperatures was observed to deteriorate glass quality, through crystallization, warping, and/or sagging. Extensive optimization of the entire process has shown that on a laboratory scale, high-optical-quality glass can be produced from both alkoxide and particulate gels. It remains to be seen whether sol-gel process will be feasible for the manufacture of high-quality glass products on a commercial scale.     

The optical response of liquid crystal cells to a low frequency driving voltage

This study investigates the optical response of liquid crystal cells to a low frequency square wave voltage of 0.1 Hz. It is found that there are three physical phenomena that dominate the overall properties of the device. The first is the discharging effect whereby the effective voltage over the liquid crystal layer decreases as a function of time; this occurs due to mobile ions being present within the liquid crystal material. The second is the charging-up of the cell where the effective voltage increases with time; this is attributed to charge separation taking place within the polyimide layer upon application of the d.c. voltage component. The third effect is cell asymmetry whereby the effective voltage depends upon the polarity of the externally applied field; this is the result of a locked-in d.c. holding voltage being present within the cell layers. These three effects are analysed in some detail with the view of developing a liquid crystal cell capable of being driven with a low frequency square wave voltage. A model of a liquid crystal cell in which the liquid crystal material can dissolve impurity ions from the alignment layers and in which the ions can then become re-adsorbed into the polyimide layer is deduced.     

Photo-Electrochemistry of Ormosil Sandwiched D-96N Bacteriorhodopsin

The application of organically modified sol–gel glass (ORMOSIL) for stabilizing D96N bacteriorhodopsin is reported. The ormosil sandwiched bacteriorhodopsin shows high stability and better photoactivity than those made under similar conditions without ormosil. Three approaches for immobilizing Bacteriorhodopsin (BR) on either quartz plate or antimony tin oxide (ATO) electrode were investigated. System-1 was made by drying the BR preparation under ambient conditions. System-2 was made by drying the same amount of BR followed by sandwiching the dried BR suspension using a transparent ORMOSIL layer whereas system-3 was made by drying the BR suspension over a transparent layer of ormosil followed by the deposition of another layer of transparent ormosil over the dried BR, thus sandwiching BR between two layers of ORMOSILS. The transparent ormosil layer was made in aqueous acidic medium using 3-aminopropyltrimethoxysilane, phenyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The characteristics of these three systems based on visual photography, UV-VIS spectroscopy (both in the presence and absence of external light) and photoelectrochemistry are reported. UV-VIS spectroscopy revealed excellent performance of BR when sandwiched between two layers of ORMOSILS (system-3) both in terms of photoactivity and stability for practical applications. The photo-electrochemistry of these three systems deposited on ATO electrodes is also reported. The photocurrent as a function of applied potential was recorded in the presence and absence of external light. The photocurrent showed increasing magnitude at negative potential and decreased from system-1 to system-3. The stability of ormosil sandwiched bacteriorhodopsin was found to exceed 1.5 years for practical applications.