A new technique for membrane characterisation: direct measurement of the force of adhesion of a single particle using an atomic force microscope

An Atomic Force Microscope (AFM) has been used to quantify directly the adhesive force between a colloid probe and two polymeric ultrafiltration membranes of similar MWCO (4000 Da) but different materials (ES 404 and XP 117, PCI Membrane Systems (UK)). The colloid probe was made from a polystyrene sphere (diameter 11 μm) glued to a V shaped AFM cantilever. Measurements were made in 10⁻² M NaCl solution at pH 8. It was found that the adhesive force at the ES 404 membrane was more than five times greater than that at the XP 117 membrane. As it allows direct quantification of particle/membrane interactions, this technique should be invaluable in the development of new membrane materials and in the elucidation of process behaviour.     

聚醚砜超滤膜法纯化电泳用Fe(OH)3溶胶

Fe(OH)3溶胶的纯化是物理化学溶胶电泳实验中最大的难题,因为传统的火胶棉半透膜渗析纯化法不仅费时费力,而且成功率很低,本文将新型的膜分离技术应用于溶胶的纯化,提出了用自制的聚醚砜超滤膜纯化溶胶的方法,实验结果表明,此法不仅纯化效果好,而且省时省力,简单易行,是替代传统方法的良好方法。     

Ultrafiltration of sodium dodecylsulfate solutions

The present paper is devoted to ultrafiltration (UF) of aqueous solutions containing micellized sodium dodecylsulfate (NaDS) through zircon membranes, following permeation data of cetyltrimethylammonium bromide (CTABr), which we have reported recently.The experimental results are analyzed using the same model of diffusion in the membrane matrix based on the thermodynamics of irreversible processes (TIP). A comparison with the classical model of resistances in series leads to a new analysis of the measured resistances in terms of membrane–permeant and permeant–permeant interactions. NaDS micelles being able to cross the membrane as permeants, in contrast with CTABr micelles, the comparison of the behaviors of anionic and cationic surfactants is worthwhile. The resistance of the membrane strongly depends on the composition of the feed. The TIP approach allows us to relate the membrane resistance to the concentrations of all the species present in the feed, namely free ions, spherical micelles and rod-like aggregates. It is shown that the resistance is highly influenced by free ions (dodecylsulfate (DS⁻) and sodium (Na⁺)), very slightly by negatively charged spherical micelles, and weakly by rod-like aggregates, also negatively charged.     

Synthesis of citrate-stabilized hydrocolloids of hydroxyapatite through a novel two-stage method: a possible aggregates-breakdown mechanism of colloid formation

Long-term stable (>2 years) hydrocolloids of hydroxyapatite (HA) were synthesized via a low-temperature (18-50 °C) reaction of aqueous ammonium phosphate with calcium nitrate in the presence of citrate ions, followed by an aging process at high temperature (80-99 °C) for 4 h. Changing the reaction and/or aging temperature seldom yielded stable HA hydrocolloids. The as-prepared hydrocolloids were desalinated through ultrafiltration where their average particle size gradually decreased, bottomed out at 100-400 μS/cm, and sharply increased in parallel with a decrease in solution conductivity. The colloid formation is most likely through a temperature-sensitive aggregates-breakdown process. During low-temperature reaction, citrate-calcium chelation bridges the growing HA particles into loose aggregates. High-temperature aging disrupts these inter-particle links and thus breaks the aggregates, imparting negative charges to the HA, forming colloidal particles stabilized by surface charge. The decrease in mean particle size during early ultrafiltration suggested that the aggregate breakdown further proceeded through desalination. In conclusion, the temperature-dependent interactions between citrate ions and calcium sites on HA particles played key roles in the synthesis and stability of the HA colloids.     

Effects of membrane hydrophilicity on the removal of a trihalomethane via micellar-enhanced ultrafiltration process

Micellar-enhanced ultrafiltration (MEUF) process was explored for obtaining pure water from an aqueous solution containing small amount of trihalomethanes (THMs). A homologous series of polyethylene glycol alkylether was used as nonionic surfactant. To understand effects of membrane hydrophilicity on the performance of MEUF process, membranes for the ultrafiltration were prepared from polysulfone blends containing various amount of a hydrophilic copolymer, poly(1-vinylpyrrolidone-co-acrylonitrile) (P(VP-AN)). An increase in the permeate flux was observed with an increase of the membrane hydrophilicity. The performance of MEUF process in removing THM and surfactant was shown to depend on the membrane characteristics, surfactant characteristics, and operating pressure. The rejections of THM and surfactant were increased with increasing hydrophobicity of surfactant and hydrophilicity of membrane. The rejections of THM examined with hydrophilic membranes were increased with increasing operating pressure, while those examined with hydrophobic membranes were decreased with increasing operating pressure. THM included in water could be removed up to 99% via MEUF process. The performance of MEUF examined with hydrophilic membranes could be explained with the rejection of micelles containing THM, while that examined with hydrophobic membranes could be explained with hydrophobic interactions between surfactant and membrane materials.     

Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M–AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd(II), and Zn(II) were carried out to characterize the stability of the metal–AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal–natural organic matter (M–NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations >485 μg L^?1 were necessary to obtain maximum exchange of the complexes Mn–NOM and Fe–NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.     

Principles of interactions in non-aqueous electrolyte solutions

In this paper a review is presented on the molecular interactions in non-aqueous media of low dielectric permittivity. Qualitative and quantitative distinctions with aqueous solutions are emphasized. The reviewed themes include dispersion forces, dissociation and association equilibria, discrimination between electrostatic and non-electrostatic interactions, ionic specificity, conductivity, electrokinetics and colloid interaction. Distinctions between so-called primitive and non-primitive interpretations and between individual and collective behavior are discussed; in these respects the colloid stability phenomena behave differently from the corresponding ones in aqueous solvents.     

The study of liposomes,lamellae and membranes using neutrons and X-rays

Advances in colloid and interface science have stimulated a renewed interest in the study of lipid–water systems. In recent years, much progress has been achieved in the domains of sample preparation and sample environments, offering the unique possibility of studying these systems under physiologically relevant conditions. In the case of neutron reflectometry, new experimental protocols allow for the unique structural determination of one-dimensional membrane profiles, while the advantages offered by synchrotron radiation (e.g., high flux and spatial resolution) make X-rays an excellent tool for addressing questions pertaining to membrane interactions. Most recently, holographic techniques are evolving so that one day they may be able to resolve, to atomic resolution, the structure of poorly crystallized membrane associated proteins.     

Oligosaccharide Shells as a Decisive Factor for Moderate and Strong Ionic Interactions of Dendritic Poly(ethylene imine) Scaffolds under Shear Forces

For better understanding and improving the non‐covalent interactions of dendritic core–shell, we evaluated the interactions of hyperbranched poly(ethylene imine) (PEI) decorated with various oligosaccharide shells with water‐soluble B vitamins, an estradiol derivative and pantoprazole. Depending on the different properties of the analyte molecules, dendritic core–shell glyco architectures showed (very) weak, moderate and strong interactions with the analyte molecules. Thus, ionic interactions are the strongest driving force for the formation of host–guest complexes. The core–shell glyco architecture is a necessary prerequisite for stable analyte/PEI complexes; the pure hyperbranched PEI did not show any sufficiently strong interactions with neutral, cationic or anionic analytes under the shear forces applied during ultrafiltration of pure aqueous solution without an adjusted pH. Thus, only robust non‐covalent interactions between analytes and the dendritic polyamine scaffold of the glycopolymer structure survive this separation step and allow isolation of stable host–guest complexes in aqueous solution.     

Characterisation of membrane surfaces: direct measurement of biological adhesion using an atomic force microscope

An atomic force microscope (AFM) in conjunction with coated colloid probe and cell probe techniques has been used to measure directly the adhesive force between both the protein bovine serum albumin (BSA) and a yeast cell at two different membranes. These were polymeric ultrafiltration membranes of similar MWCO (4000 Da) but of different materials (ES 404 and XP 117, PCI Membrane Systems, UK). The XP 117 membrane is made from a mixture of polymers chosen with the aim of achieving low fouling. The BSA was adsorbed on a 5 μm silica colloid probe formed from a tipless V-shaped AFM cantilever. The cell probe was created by immobilising a single yeast cell on such a tipless cantilever. Measurements were made in 10⁻² M NaCl solution. It was found for both protein and cell systems that the adhesive force at the ES 404 membrane was greater than that at the XP 117 membrane. The paper shows that coated colloid probe and cell probe techniques can provide useful means of directly quantifying the adhesion of biological materials to membrane surfaces.     

Efficient polymers in conjunction with membranes to remove As(V) generated in situ by electrocatalytic oxidation

Electrochemistry and ultrafiltration membrane methods (electro‐oxidation and liquid phase polymer based retention technique LPR, respectively) were coupled to remove As(III) inorganic species from aqueous solutions. Our main objective was to achieve an efficient extraction of arsenic species by associating a polymer‐assisted liquid phase retention procedure, based on the As(V) adsorption properties of cationic water‐soluble polymers, with the electrocatalytic oxidation process of As(III) into its more easily removable analog As(V). The exhaustive oxidation of As(III)–As(V) was readily performed in high yield at iridium oxide film modified carbon felt electrodes in the presence of different water‐soluble poly(quaternary ammonium) salts acting also as supporting electrolyte. The progress of the macro‐scale oxidation of As(III)–As(V) was followed using iridium oxide film modified glassy carbon electrodes. Finally, a study on arsenic retention by LPR‐technique performed on fully oxidized solutions of arsenic, showing that complete (100%) retention of the arsenic could be achieved using a 20:1 polyammonium:As(III) mole ratio. Copyright © 2009 John Wiley & Sons, Ltd.     

A comparative economic analysis of copper removal from water by ligand-modified micellar-enhanced ultrafiltration and by conventional solvent extraction

In ligand-modified micellar-enhanced ultrafiltration (LM-MEUF), a surfactant and a ligand are added to an aqueous solution containing ions of like charge. The ligand forms a complex with the target ion of interest and becomes incorporated in the micelle. This solution is then treated by an ultrafiltration process with membrane pore sizes small enough to reject the micelles and their solubilized metal–ligand complex. Previous studies have demonstrated the technical feasibility of LM-MEUF with copper rejection exceeding 99% with no removal of calcium using several different ligands. The ability to regenerate the surfactant/ligand for reuse has also been shown. In this study, an economic analysis of LM-MEUF (with regeneration) for a 1×10⁵ gal/day unit is reported. The effects of important parameters are investigated; including feed surfactant, ligand, and copper concentrations. The results from the sensitivity analysis are used to compare the cost of LM-MEUF for copper removal and recovery to the conventional copper solvent extraction process. The comparative economic analysis indicates a 17% higher capital and a 43% higher operating cost for LM-MEUF process compared to the solvent extraction process.     

Ultrafiltration of surfactant solutions

The ultrafiltration of colloid solutions containing hexadecyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and alkylpolyglucoside (APG) through hydrophilic membranes with a 10,000 mol wt cut-off from regenerated cellulose was studied. The effects of experimental conditions on the permeate flux and secondary resistance were determined. It was found that both CTAB and APG were convenient surfactants for ultrafiltration, as high permeability of their solutions was observed. The secondary resistance was always significantly lower than the resistance of the membrane. Additionally, electrolytes had a relatively weak negative effect upon ultrafiltration fluxes. SDS was the least convenient surfactant due to formation of a gel layer, susceptibility of its colloid solutions to electrolyte content, and a high secondary resistance. The concentration of the surfactant in the permeate could increase above critical micelle concentration, especially under conditions inducing high polarization. Migration of CTAB on the surface of pores seemed responsible for that transfer.     

Micellar enhanced ultrafiltration of cadmium

The preconcentration of cadmium from aqueous colloid solution containing 8-hydroxyquinoline as extractant, laurylsulphate natrium as surfactant,n-butanol as co-surfactant was performed using micellar ultrafiltration technique. Filters with different pore size and materials were used to achieve a separation from liquid solutions. The cadmium recoveries depending on different conditions (pH, concentration of surfactant) were determined and the results are explained in the terms of colloidal parameters in the compare with the classical solvent extraction.     

Membrane fouling and cleaning in ultrafiltration of wastewater from banknote printing works

The hollow fiber blend membrane, fouled by plant wastewater from banknote printing works, was characterized with SEM and the fouling elements were investigated by EDX. Based on analysis results, fouling process in ultrafiltration was simulated by using the model substances, which exist in the wastewater from banknote printing works, such as Turkey red oil, sodium hydroxide and calcium ion. It is observed that the reaction between Turkey red oil and calcium ion forms sediments, which leads to the beginning of membrane fouling. Furthermore, a four-step cleaning method, including de-ionized water cleaning, hydrochloric acid (0.1N) aqueous solution cleaning, second de-ionized water cleaning and sodium hydroxide (1 wt.%) aqueous solution cleaning, was used to clean the seriously fouled membrane in both lab and plant scale (membrane areas were 0.0157 and 80 m², respectively) experiments. The results show that the cleaning method is effective. The membrane surface after cleaning was also analyzed by SEM/EDX and the foulants in the cleaning solutions were identified by TOC and ICP. According to these experimental results, the mechanisms of membrane fouling and cleaning were proposed. The four-step cleaning method has been widely used in the ultrafiltration of wastewater from banknote printing works.     

Quinone-based molecular electrochemistry and their contributions to medicinal chemistry: A look at the present and future

Molecular electrochemistry is closely linked to life sciences. Electron transfers play important roles in the bioactivation of redox-active drugs, in their metabolism/catabolism, and in their targeted release at precise destinations and frequently promote their ligand–target interactions. Altogether, this rich chemistry and the complexity of cellular environments and biocompartmentation often impede full investigation in situ of the whole chain of processes that sustain their therapeutic applications. Conversely, electrochemical ex situ investigations of drug properties and interactions performed in aqueous/aprotic/micellar/membrane/cell-mimetic media, combined with in vitro and in vivo data, are expected to provide extremely useful information on these processes. Therein, considering the ubiquitous case of quinones, we exemplified how such strategies allow controlling their beneficial or negative impact on cellular environments.     

Antioxidant activity of daidzein, a natural antioxidant, and its spectroscopic properties in organic solvents and phosphatidylcholine liposomes

Daidzein, one of major isoflavones found in soybeans, has a wide spectrum of physiological and pharmacological functions. The observed biological effects involve its interactions with lipid bilayers, usually detected by indirect methods. In this study we use the native fluorescence of daidzein to report changes observed during its interactions with organic solvents and in a phosphatidylcholine membrane.We have investigated interactions of daidzein with lipid bilayers of egg phosphatidylcholine (PC) by absorption and fluorescence methods. The data obtained indicate emission arises from the conjugate anion in excited singlet state. The fluorescence is found to increase with the basicity of the solution and the polarity of the solvent. An increase in fluorescence anisotropy in the presence of membranes suggests partial incorporation of daidzein molecules into the bilayer. Two fluorescence lifetime components, 1.5 ns and 3.5 ns, reflects the partition of daidzein between aqueous and membrane environments, respectively. On the basis of the obtained spectroscopic data we conclude that up to 15% of daidzein is located in hydrophilic region of the membrane whereas the rest is distributed in aqueous bulk and aqueous/membrane interface.For studying the antioxidant activity of daidzein against lipid peroxidation initiated by AAPH the molecule of C11-BODIPY581/591 has been used as a fluorescent oxidation indicator. The results show that the presence of daidzein anions in the membrane interface increases the inhibitory effect on lipid peroxidation compared to the neutral form of daidzein.     

Hydration energy or hydration force? Origin of ion-specificity in ion selective electrodes

The origin of ion-specificity (also known as Hofmeister effect) in potentiometric ion selective electrodes (ISE) with polymeric membranes has been traditionally assigned to the differences in lipophilicities of ions, with hydration energies described in the framework of Born theory as being of purely electrostatic nature. This is in clear contrast to the current understanding of the Hofmeister effect in colloid and interface science, where it is viewed as resulting from an interplay between the electrostatic and non-electrostatic interactions, the latter often referred to as “hydration” forces. The two approaches to ion-specificity in ISE, simplistically termed “hydration energy” (ion partitioning between an aqueous phase and the ISE membrane) and “hydration force” (ion adsorption from an aqueous phase to the electrically charged ISE membrane) are described and compared. Two major conclusions are drawn: i) ion-specificity can be included in both approaches, although it is more natural within the “hydration force” approach with ion-surface interactions; ii) both ion partitioning into, and ion adsorption onto the ISE membrane should be considered in order to fully understand the origin of ion-specificity in ISE.     

Influence of inclination on gas-sparged cross-flow ultrafiltration through an inorganic tubular membrane

The effect of membrane inclination on the flux of single-phase or gas–liquid two-phase ultrafiltration in a tubular membrane has been investigated. Experimental result shows that membrane inclination has a significant enhancement on the flux of two-phase ultrafiltration operated at slug flow pattern. As the angle of inclination from the horizontal increases, the flux increases, reaches a maximum, and then decreases. The flux may be enhanced more than 1.5 when the membrane is inclined from 0 to 50°. The flux enhancement due to membrane inclination increases with increasing the gas velocity, the feed concentration, and the transmembrane pressure, while it decreases with increasing the liquid velocity. The optimal inclination angle of the membrane in a slug-flow ultrafiltration is close to 50°. An equation for determining the optimal inclination angle was also proposed in this work.