A new route for the fabrication of TiO2 ultrafiltration membranes with suspension derived from a wet chemical synthesis

Titania ultrafiltration membranes were successfully fabricated by a new route, which was directly derived from the nanoparticles suspension that was the intermediate product prior to dry and calcine in the synthesis of nanoparticle by a wet chemical method. The morphology and the crystal structure of the prepared membrane were analyzed by SEM and XRD. The effect of various dipping time on the membrane thickness was investigated. The rejection of the bovine serum albumin (BSA, 67,000 Da) was used to evaluate the separation characteristics of these membranes, and the relationship between the dipping time and the optimization thickness of the membrane was built on the base of the data of the pure water flux. SEM images showed that the surface of the membrane was defect-free and XRD revealed that the titania crystalline phase was pure anatase. The membrane thickness increased linearly with the square root of the dipping time and the dipping time of 30 s was necessary to form a defect-free titania layer on the top of supports. The titania layer derived from the dipping time of 30 s could be of thickness of 5.9 μm and an average pore size of 60 nm. The pure water permeability of the membrane was 860 × 10⁻⁵ L/(m² h Pa) (860 L/(m² h bar)), and the BSA rejections of the membranes prepared reached to 90% after 20 min running.     

Chiral separation of phenylalanine in ultrafiltration through DNA-immobilized chitosan membranes

Ultrafiltration experiments for the chiral separation of racemic phenylalanine were performed with DNA-immobilized chitosan membranes having various pore sizes. Atomic analysis on the membranes showed that the chitosan membranes covalently bound six times more DNA than the cellulose membranes used in our previous study [A. Higuchi, Y. Higuchi, K. Furuta, B.O. Yoon, M. Hara, S. Maniwa, M. Saitoh, K. Sanui, Chiral separation of phenylalanine by ultrafiltration through immobilized DNA membranes, J. Membr. Sci. 221 (2003) 207–218]. d-Phenylalanine preferentially permeated through DNA-immobilized chitosan membranes with a pore size <6.4 nm [molecular weight cut-off (MWCO) <67,000]. The binding affinity of a specific enantiomer due to the pore size of the DNA-immobilized membranes regulated the preferential permeation of the enantiomer through the membranes. l-Phenylalanine was adsorbed on the DNA-immobilized chitosan membranes with a pore size <6.4 nm (MWCO < 67,000), while there was little difference between the adsorption of d-phenylalanine and l-phenylalanine on the membranes with a pore size >6.4 nm (MWCO > 67,000). The DNA-immobilized chitosan membranes were categorized as channel type membranes.     

Flow-injection chemiluminescence detection for studying protein binding for drug with ultrafiltration sampling

The novel flow chemiluminescence (CL) system for determination of pipemidic acid was proposed, which was based on the sensitizing effect of pipemidic acid on the CL oxidation of sulfite by KMnO₄ in acid media. Combined with the technique of ultrafiltration, the flow-injection CL system was applied to study in vitro the bovine serum album (BSA) binding of pipemidic acid. The estimated association constant (K) and the number of the binding site (n) on one molecule of BSA were 8.81×10⁴ l/mol and 0.94, respectively. The method provided a fast and simple technique for the study of drug-protein interaction.     

分离液体的膜

本文概述了7种以高分子为膜材料、用于混合液体分离的膜分离过程,即离子交换膜与电渗析、反渗透、超滤、微孔过滤、膜萃取、渗透汽化和膜蒸馏。对其原理、高分子膜材料、应用和发展趋向作了简要介绍;并阐述了我国膜分离发展的现状和展望。     

CE-LIF method for the separation of anthracyclines: application to protein binding analysis in plasma using ultrafiltration

Anthracyclines are chemotherapeutic drugs that are widely used in the treatment of cancers such as lung and ovarian cancers. The simultaneous determination of the anthracyclines, daunorubicin, doxorubicin and epirubicin, was achieved using CE coupled to LIF, with an excitation and emission wavelength of 488 and 560 nm, respectively. Using a borate buffer (105 mM, pH 9.0) and 30% MeOH, a stable and reproducible separation of the three anthracyclines was obtained. The method developed was shown to be capable of monitoring the therapeutic concentrations (50-50 000 ng/mL) of anthracyclines. LODs of 10 ng/mL, calculated at an S/N = 3, were achieved. Using the CE method developed, the in vitro protein binding to plasma was measured by ultrafiltration, and from this investigation the estimated protein binding was determined to be in the range of 77-94%.     

Modification of polyethersulfone ultrafiltration membranes with phosphorylcholine copolymer can remarkably improve the antifouling and permeation properties

The synthesized phosphorylcholine copolymer composed of 2-methacryloyloxyethylphosphorylcholine (MPC) and n-butyl methacrylate (BMA), blended with polyethersulfone (PES), was used to fabricate antifouling ultrafiltration membranes. Water contact angle measurements confirmed that the hydrophilicity of the MPC-modified PES membranes was enhanced to certain extent. X-ray photoelectron spectroscopy (XPS) analysis verified the substantial enrichment of MPC at the surface of the MPC-modified PES membranes. The adsorption experiments indicated that the adsorption amounts of bovine serum albumin (BSA) on the MPC-modified PES membranes were dramatically decreased in comparison with the control PES membrane. Ultrafiltration experiments were carried out to investigate the effect of MPC modification on the antifouling and permeation properties of the PES membranes, it was found that the rejection ratio of BSA was decreased, the flux recovery ratio was remarkably increased, and the degree of irreversible fouling decreased from 0.46 to 0.09. In addition, the MPC-modified PES membranes could run several cycles without substantial flux loss.     

Nonlinear two-phase equilibrium model for the binding of arsenic anions to cationic micelles

The binding of arsenic ions to cationic cetylpyridinium chloride (CPC) micelles has been investigated using the semiequilibrium dialysis (SED) technique. In SED experiments, it has been shown that CPC micelles are very effective in binding arsenic ions in the retentate. At the studied pH (pH 8), the unbound and bound arsenic exists primarily as divalent anions (HAsO₄²⁻) while CPC molecules exist as monovalent cations. Therefore, arsenic ions are bound electrostatically to the cationic micelle. The resultant colloid is large enough not to pass through the dialysis membrane, producing a rejection greater than 99.59%. The concentration of the unbound arsenic anions passing through the dialysis membrane is practically the same as the permeate concentration of these species in the analogous micellar-enhanced ultrafiltration (MEUF) experiments. Therefore, a nonlinear equilibrium model which combines thermodynamic relations, charge balance equations, and material balance equations with the Oosawa two-phase polyelectrolyte theory has been developed to correlate the binding of arsenic to CPC micelles in SED and MEUF. It was shown that the equilibrium model successfully accounts for the experimental data in both SED and MEUF in the absence and presence of monovalent (HCO₃¹⁻) and divalent co-ions (HPO₄²⁻). Because of their small sizes (less than 10 nm), micelles should retain their equilibrium shapes in the presence of hydrodynamic shear typically attained in most dynamic processes. Therefore, the equilibrium model can be used to predict separation efficiencies in other ultrafiltration units such as in crossflow ultrafiltration processes.     

Comparison of physico-chemical pretreatment methods to seawater reverse osmosis: Detailed analyses of molecular weight distribution of organic matter in initial stage

In desalination, effective pretreatment is the key to reduce membrane fouling that occurs during the seawater reverse osmosis (SWRO) process. However, it is difficult to compare the flux decline after different pretreatments using a small-scale reverse osmosis filtration unit. In this study, we successfully evaluated the effect of pretreatment on SWRO in terms of molecular weight distribution (MWD) of seawater organic matter (SWOM) after 20 h of SWRO operation. Microfiltration (MF), ultrafiltration (UF), ferric chloride (FeCl₃) flocculation and powdered activated carbon (PAC) adsorption, were used as pretreatment. The effluents and the retentates after each pretreatment and 20 h of SWRO operation were characterized in terms of MWD.Although the normalized flux of SWRO showed similar flux decline (J/J₀ = 0.17) with/without pretreatment, SWOM concentration in the retentates after different pretreatments was different in quantity and it increased linearly with time. The slope of the SWOM increase was 0.110, 0.096, 0.077 and 0.059 after MF, FeCl₃ flocculation, UF and PAC adsorption pretreatments, respectively. MW peaks for the seawater used in this study consisted of 1200 Da (biopolymers), 950 Da (fulvic acids), 650 Da (hydrolysates of humic substances), 250 Da (low MW acids) and 90 Da (low MW neutrals and amphiphilics). FeCl₃ flocculation preferentially removed 1200 Da (biopolymers), while PAC adsorption mostly removed 950 Da (fulvic acids). UF and NF removed only a marginal amount of relatively large organics, while RO removed the majority of organics. The intensity of 1200, 950, 650 and 250 Da MW in the RO retentates increased with the RO operation time. The organics of MW around 1200 Da (biopolymers) had a relatively low rate of increase with time compared with those of lower MW. This suggests that the SWOM of 1200 Da MW was preferentially retained on the membrane surface.     

Preparation and characterization of polyaniline/polysulfone nanocomposite ultrafiltration membrane

Novel nanocomposite membrane was prepared through the filtration of polyaniline (PANI) nanofiber aqueous dispersion with polysulfone (PS) ultrafiltration (UF) membrane. Scanning electron microscope (SEM) images showed that PANI nanofiber layer was formed on the PS membrane surface. Atomic force microscopy (AFM) analysis indicated that the nanocomposite membrane had rougher surface than the PS substrate membrane. Compared with the PS substrate membrane, the nanocomposite membrane had much better permeability for the good hydrophilicity of PANI nanofiber layer, and had almost the same rejection performance. In addition, the nanocomposite membrane had positive surface potential under acidic condition because PANI could be protonated easily by acid. During the filtration of BSA solution, the nanocomposite membrane showed much better antifouling performance than the substrate membrane for the hydrophilicity and steric hindrance effect of its nanofiber layer. Moreover, under acidic solution condition, strong electrostatic repulsion between PANI nanofibers and BSA existed and improved membrane antifouling performance further.     

Coagulation and ultrafiltration: Understanding of the key parameters of the hybrid process

A hybrid coagulation–ultrafiltration process has been investigated to understand membrane performance. Coagulation prior to ultrafiltration is suspected to reduce fouling by decreasing cake resistance, limiting pore blockage and increasing backwash efficiency. Coagulation followed by tangential ultrafiltration should gather the beneficial effects of particle growth and cross-flow velocity. Our study aims at determining the key parameters to improve membrane performance, by describing floc behaviour during the hollow fibre ultrafiltration process. Flocs encounter a wide range of shear stresses that are reproduced through the utilization of different coagulation reactors. Performing a Jar-test enables the formation of flocs under soft conditions, whereas Taylor-Couette reactors can create the same shear stresses occurring in the hollow fibres or in the pump. Synthetic raw water was made by adding bentonite into tap water. Five organic coagulants (cationic polyelectrolytes) and ferric chloride were selected. Floc growth was thoroughly monitored in the different reactors by laser granulometry. Coagulation–ultrafiltration experiments revealed different process performance. The effect on the permeate flux depended on the coagulant used: some coagulants have no influence on permeate flux, another enables a 20% increase in permeate flux whereas another coagulant leads to a decrease of 50%. Flocs formed with ferric chloride do not resist shear stress and consequently have no influence on permeate flux. These results show the necessity to create large flocs, but the size is not sufficient to explain membrane performance. Even if flocs show a good resistance to shear stress, a high compactness (D_f = 3) will lead to a dramatic decrease of permeate flux by increasing the mass transfer resistance of the cake. On the contrary, flocs less resistant to shear stress, then smaller and also more open have no effect on permeate flux. An optimum was quantified for large flocs, resistant enough to shear stress facilitating flow between aggregates.