HEMA‐grafted chitosan for dialysis membrane applications

Chitosan was graft copolymerized with HEMA (2‐Hydroxyethylmethacrylate) for the development of blood‐compatible dialysis membranes. The permeation characteristics of HEMA‐grafted chitosan films for four different solutes creatinine, urea, glucose, and albumin was studied in vitro at 37°C for assessment of the suitability as dialysis membranes. The grafted film CH‐12.5 composition (425% grafting) showed very high permeation to creatinine by reaching the equilibrium within 45 min. The compositions CH‐7.5 and CH‐12.5 showed excellent permeation to glucose when compared to virgin chitosan films. In the case of urea permeation, all the grafted compositions exhibited higher percent permeation than the virgin chitosan films. The copolymer films CH‐7.5 and CH‐12.5 showed enhanced permeability for the high molecular weight solute, albumin. The other grafted copolymer compositions followed almost the same trend as that of chitosan for the low molecular weight solutes as well as the high molecular weight solute. The copolymer films were also found to be highly blood compatible, noncytotoxic, and biodegradable. Hence, the need for developing blood‐compatible chitosan membranes with desirable permeability properties is achieved by the graft copolymerization of HEMA onto chitosan. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2960–2966, 2006     

An improved approach for determining permeability and diffusivity relevant to controlled release

A new approach combining time lag and mass balance for determining the kinetic parameters in controlled release was proposed in order to minimize measurement errors due to actual experimental conditions deviating from idealities under which the time lag and mass balance analyses were developed. Basically, the permeation data were pre-screened for analysis with time lag and mass balance methods separately, and criteria for data screening were proposed. The upper time limit of short-time permeation data suitable for analysis with the time lag method was determined based on the extent of concentration variations across the membrane, and the onset time point of the long-time permeation data for analysis with the mass balance method was determined based on the time lag of the system. The permeation of ciprofloxacin hydrochloride through chitosan membranes was chosen as a model system to demonstrate the validity of this approach for evaluation of permeability and diffusivity.     

Two new types of copolymer membranes controlling clonidine zero‐order release

Two new types of membranes were synthesized by UV curing in our laboratory. The first type of membrane was made of three monomers: 2‐hydroxy‐3‐phenoxypropylacrylate(A), 4‐hydroxybutyl acrylate(B), and 2‐methyl‐2‐nitropropyl methacrylate(C1). The second type of membrane was made of the same monomers A and B, and 2‐butoxyethyl methacrylate(C2). Permeation properties of clonidine releasing through two new types of copolymer membranes were studied. The effects of the ratios of monomers, the thicknesses of membranes, and the concentration of clonidine on the permeation rates were studied. It was found that both copolymer membranes could control clonidine zero‐order release. The permeation rates of the first optimized membrane were linearly dependent on the square root of the drug concentration. The permeation rates of the second optimized membrane had no significant difference when the concentration of clonidine varied in the range of 3.0–5.0 mg mL^?1. Furthermore, both optimized membranes were characterized by FTIR, DSC, and SEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Poly(2‐hydroxyethylmethacrylate)/chitosan dye and different metal‐ion‐immobilized interpenetrating network membranes: Preparation and application in metal affinity chromatography

Composite membranes were synthesized with 2‐hydroxyethylmethacrylate and chitosan (pHEMA/chitosan) via an ultraviolet‐initiated photopolymerization technique in the presence of an initiator (α,α′‐azobisisobutyronitrile). The interpenetrating network (IPN) membranes were improved by the immobilization of dye molecules via hydroxyl and amino groups on the membrane surfaces from the IPNs. A triazidine dye (Procion Green H‐4G) was covalently immobilized as a ligand onto the IPN membranes. The protein showed various affinities to different chelated metal ions on the membrane surfaces that best matched its own distribution of functional sites, resulting in a distribution of binding energies. In support of this interpretation, two different metal ions, Zn(II) and Fe(III), were chelated with the immobilized dye molecules. The adsorption and binding characteristics of the different metal‐ion‐chelated dye‐immobilized IPN membranes for the lysozyme were investigated with aqueous solutions in magnetically stirred cells. The experimental data were analyzed with two adsorption kinetic models, pseudo‐first‐order and pseudo‐second‐order, to determine the best fit equation for the adsorption of lysozyme onto IPN membranes. The second‐order equation for the lysozyme–dye–metal‐chelated IPN membrane systems was the most appropriate equation for predicting the adsorption capacity for all the tested adsorbents. The reversible lysozyme adsorption on the dye‐immobilized and metal‐ion‐chelated membranes obeyed the Temkin isotherm. The lysozyme adsorption capacity of the pHEMA/chitosan dye, pHEMA/chitosan dye–Zn(II), and pHEMA/chitosan dye–Fe(III) membranes were 2.54, 2.85, and 3.64 mg cm^?2, respectively. The nonspecific adsorption of the lysozyme on the plain pHEMA/chitosan membrane was about 0.18 mg cm^?2. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1843–1853, 2003     

Separation of Water/Ethanol Vapor Mixtures through Chitosan and Crosslinked Chitosan Membranes

Abstract

The separation of water/ethanol vapor mixtures through chitosan membranes and crosslinked chitosan membranes was studied by means of the vapor permeation technique. The permeation performance was discussed in terms of separation factor and permeation flux. Crosslinking the chitosan membrane by glutaraldehyde enhanced the selectivity. The highest separation factor obtained was 6000 for a crosslinked chitosan membrane with a degree of deacetylation of 100%.     

Selective permeabilities of chitosan-acetic acid complex membrane and chitosan-polymer complex membranes for oxygen and carbon dioxide

Summary Chitosan-acetic acid complex membrane and several chitosan-polymer complex membranes have been prepared and the gas permeabilities of these membranes have been examined. It has been found that chitosan-acetic acid complex membrane shows high permselectivities for oxygen and carbon dioxide, and synthetic polymers can modify the permeation behavior of chitosan membrane for oxygen and carbon dioxide. The separation factor CO₂/O₂ of these membranes were much smaller than unity, indicating possible applications for the preservations of fruits and vegetables. It has been noticed that the permeation behaviors of these membranes are markedly influenced by metal ions added into the membranes and the membranes have good mechanical strength.     

Characteristics of permeation and separation of aqueous alcoholic solutions with chitosan derivative membranes

Permeation and separation characteristics for the feed vapours from aqueous alcoholic solutions through chitosan derivative membranes such as chitosan acetate (GA-ChitoA), chitosan (GA-Chito), and carboxymethyl chitosan acetate (GA-CM-ChitoA) membrane crosslinked with glutaraldehyde were investigated by evapomeation. The GA-Chito and GA-CM-ChitoA membranes prepared from casting solutions containing an optimum amount of glutaraldehyde showed a high permeation rate and high water permselectivity for an azeotropic composition in an aqueous ethanol solution. The permselectivity for water through the GA-CM-ChitoA membrane in evapomeation was in the order of aqueous solutions of methanol < ethanol < 1-propanol. The effect of the chemical and physical structure of these hydrophilic membranes on the permeation and separation characteristics is discussed.     

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

Poly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL^?1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of Chitosan Membranes in Separation of Heavy Metal Ions

Abstract

The authors present an application of chitosan membranes for the removal of heavy metal ions. Investigations covered membranes produced by phase inversion. Additionally, separation properties of acetylated membranes were tested. Low-viscous chitosan produced by the Sea Fisheries Institute—Poland was used in the experiments. The investigations were carried out for the transition metal ions Cr(VI), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II). A method for metal ions separation by means of chitosan membranes was proposed. The metal ions were complexed in the membrane during ultrafiltration of the solution. The separation ability of the membranes was investigated for individual metal ions and for a mixture. The effect of the pH of the solution on separation properties of membranes was determined. The concentration of metal ions was investigated by the method of inductively coupled plasma (ICP) atomic emission spectrometry. The investigations show the suitability of chitosan membranes produced by the phase inversion method for the removal of metal ions.     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The Study of Ethanol/Water Vapors Permeation through Sulfuric Acid Cross-Linked Chitosan Magnetic Membranes

Sulfuric acid cross-linked chitosan membranes filled with a different amount of magnetite, were prepared. The permeation behavior of ethanol and water vapors in vapor permeation experiments were studied. Permeation rates were measured. Mass transport coefficients were evaluated. The study has been carried out to determine the influence of magnetic powder dispersed inside of the chitosan membrane on ethanol-water separation. The diffusion, fluxes, and permeation coefficients increased with greater amount of magnetite content. The separation factor increased with increasing flux and the best results were achieved for the membrane containing 15% w/w magnetite. The research allows optimizing the preparation procedure of chitosan magnetic membranes cross-linked by sulfuric acid with the best permeation properties.     

Theoretical Analysis of Copper-Ion Extraction through Hollow Fiber Supported Liquid Membranes

Abstract

An understanding of the extraction of metal ions through hollow fiber supported liquid membranes is important for the design of such systems. In this paper, copper-ion extraction through hollow fiber supported liquid membranes containing D2EHPA as a carrier agent is analyzed. Both a rigorous model and a simple model with varied permeation coefficients for the system are proposed. The once-through mode is first modeled and the parametric effects on the extraction rate are discussed. The recycling mode is then modeled. A comparison between the rigorous model and the simple model with varied/constant permeation coefficients is made. From the models it is found that the permeation coefficient is a function of copper ion concentration.     

Preparation of novel ZSM‐5 zeolite‐filled chitosan membranes for pervaporation separation of dimethyl carbonate/methanol mixtures

Novel mixed matrix membranes were prepared by incorporating ZSM‐5 zeolite into chitosan polymer for the pervaporative separation of dimethyl carbonate (DMC) from methanol. These membranes were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) to assess their morphology, intermolecular interactions, and crystallinity. Sorption studies indicated that the degree of swelling for zeolite‐filled membranes increased with zeolite content in the membrane increasing and the separation selectivity of DMC/methanol was dominated by solubility selectivity rather than diffusivity selectivity. The characteristics of these membranes for separating DMC/methanol mixtures were investigated by varying zeolite content, feed composition, and operating temperature. The pervaporation separation index (PSI) showed that 5 wt % of ZSM‐5 zeolite‐filled membrane gave the optimum performance in the PV process. From the temperature‐dependent permeation values, the Arrhenius activation parameters were estimated. The resulting lower activation energy values obtained for zeolite‐filled membranes contribute to the framework of the zeolite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Separation of liquid mixtures by using polymer membranes. III. Grafted poly(vinyl alcohol) membranes in vacuum permeation and dialysis

A series of poly(vinyl alcohol) membranes were modifed by radiation-induced graft copolymerization with acrylic acid and methacrylic acid monomers. These grafted poly(vinyl alcohol) membranes were then tested for their separation and permeability characteristics in vacuum permeation and dialysis experiments. The permselectivity of the membranes toward methanol and water was studied on a vacuum permeation apparatus at 30, 40, and 50°C. The permeation process was found to be a temperature-activated process. The logarithm of the permeation rate varied linearly with the reciprocal of the absolute temperature. The permeability of the grafted membranes was found to increase with the degree of grafting, with no appreciable selectivity toward water in binary mixtures. The acrylic acid-grafted membranes generally showed greater improvement in permeability than the methacylic-grafted membranes. The permeability of the grafted membranes toward methanol, sodium chloride, urea, creatinine, and uric acid was studied in a dialyzer. In all cases, the grafted membranes showed an improved permeability toward these solutes over the commercial poly(vinyl alcohol) membranes. The dialysis results were then compared with those obtained for dialysis-grade cellophane membranes. For the case of sodium chloride, urea, and methanol, the permeability of the grafted membranes was comparable to that of cellophane. A comparison of commercial and grafted poly(vinyl alcohol) membranes in their permeability toward ionic solutes exhibited somewhat anomalous behavior in that the permeability of the commercial membranes was higher than that of the grafted membranes. This related to the ionic nature of the modified membrane. The permeability coefficients determined in the dialysis experiments were found to be directly related to the degree of hydration of the grafted membrane. This behavior was attributed to changes in the size and shape of voids within the membrane structure.     

High gas permeability in open-structure membranes

For most polymeric membranes, the gas permeability coefficient (P) is often interpreted as the product of diffusivity (D) and solubility (S) of a penetrant gas in the polymer (P=D S). The basic assumption is that molecular diffusion is primarily responsible for mass transport in the membrane permeation process. However, for some open structure membranes, such as poly(1-trimethylsilyl-1-propyne) [PTMSP] or poly(dimethylsiloxane) [PDMS], the high permeabilities of some gases yield much higher diffusivities when calculated from the above relationship (P=D S) than when calculated by using the direct kinetic measurement of diffusivity. It is hypothesized that this discrepancy is due to the convective transport of gas molecules through such open structured polymers. In most cases, the convective contribution to mass transport through membranes is negligible. However, for polymer membranes with high free volume, such as PTMSP, whose free volume fraction is 20 to 25%, the convective term may dominate the permeation flux. In this study, a non-equilibrium thermodynamic formalism is employed to properly treat the diffusion term and convective term that constitute the Nernst-Planck equation. The current analysis indicates that the total permeation flux, which consists of a diffusion term and a convective term, agrees well with the experimental data for several permeation systems: pure components propane and n-butane/PTMSP, pure gas hydrogen/PTMSP, and mixed gas hydrogen/PTMSP. Also, the permeation systems of a nonporous rubbery membrane, PDMS, and eight organophosphorus compounds were included in the study. It is recommended that the proposed model be validated by using other polymers with high free volumes and high permeabilities of gases and vapors, such as poly(1-trimethylgermyl-1-propyne) [PTMGeP] and poly(4-methyl-2-pentyne) [PMP]. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Propranolol hydrochloride release behaviour of crosslinked chitosan membranes

Chitosan membranes of 20 μm thickness were prepared by a solvent evaporation technique and crosslinked with different concentrations of glutaraldehyde to obtain membranes of various degrees of crosslinking. These membranes were characterized by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and tensile strength studies. The effect of crosslinking on the permeability of membranes to propranolol hydrochloride was evaluated by permeation studies conducted in static glass diffusion cells. A decrease in the thermal stability of chitosan membranes due to crosslinking was observed. The tensile strength of the membranes was improved by crosslinking. The introduction of crosslink points within the membrane reduced its permeability to propranolol hydrochloride as evidenced by decreased permeability and diffusion coefficients. Permeability studies revealed the operation of a pore mechanism in the transport of hydrophilic agents such as propranolol hydrochloride through chitosan and crosslinked chitosan membranes.     

Percutaneous absorption of volatile solvents following transient liquid exposures II. Ethanol

The permeation of neat ethanol through split-thickness cadaver skin was measured in non-occluded Franz cells placed in a fume hood. The test compound spiked with ¹⁴C radiolabel was applied to skin using four doses ranging from 6.33 to 50.6 μL/cm² (5-40 μL over an area of 0.79 cm²). Additional gravimetric experiments were conducted with ethanol and benzene to determine the evaporation mass transfer coefficient. The experimental data were analyzed by non-linear regression analysis using a previously developed diffusion model in order to ascertain the optimal values of two adjustable parameters, the fractional deposition depth (f_dep) and the permeant diffusivity inside the stratum corneum (D_SC). Constant diffusivity and variable diffusivity models were considered. Both models were able to describe the combined observations from absorption data from three of the four applied doses. The best correlation between the experimental data and model predictions was observed with the variable diffusivity model.     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

Alginate‐coated chitosan membrane for guided tissue regeneration

Chitosan membranes were first prepared by a thermally induced phase separation method and then alginate was coated on one side of the membranes by a modified dialysis apparatus to prepare alginate/chitosan membranes (A/C membranes). Electron spectroscopy for chemical analysis (ESCA), scanning electron microscope, and contact angle measurements were conducted to evaluate the surface characteristics. The mechanical strength, degradation behavior, and cell adhesion test were performed to evaluate the feasibility of using A/C membrane in guided tissue regeneration applications. The results revealed that alginates could effectively be coated onto the chitosan membrane. As observed in ESCA results, the N‐atomic emission peak was decreased from originally 6.2% on the untreated chitosan surface to 2% on the alginate‐treated surface. The contact angle decreased on the alginate‐modified side substantially, compared with the untreated side (from 88.4° to 34.2°). The A/C membrane had a higher water content of 71.8% in comparison to the chitosan membrane of 61.8%. Consequently, A/C membrane became stiffer and had a higher Young's modulus and strength. After a 30‐day in vitro shaking test, the weight of membranes was degraded to about 75% from the original. The 3T3 fibroblast cells showed less adhesion to alginate‐modified side as compared to the untreated chitosan‐side in cell adhesion test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4528–4534, 2006     

Sorption of sulfur mustard and its oxygen analog in black and nonblack-filled butyl rubber membranes

Butyl rubber (IIR) membranes containing a 0–50% volume fraction of carbon black (GPF N660) or nonblack fillers (talc/precipitated CaCO₃/fullers earth) were prepared by solution casting and evaluated for permeation resistance to the vesicant, bis(2-chloroethyl)sulfide, or sulfur mustard (SM) and its oxygen analog (OA), bis(2-chloroethyl)ether. The diffusivity of the chemicals was determined from the breakthrough time (BTT), obtained using the spot disc test and a gravimetric method. The permeation parameters, calculated from the sorption data, were used to determine an optimum filler content for maximum protection against SM. To investigate the effect of carbon loading on the permeation properties of IIR, the permeation of SM and OA in carbon-loaded black membranes was compared with nonblack membranes and interpreted in terms of the dispersion of carbon in the membranes. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 503–511, 1998