Behavior of immobilized glucose oxidase on membranes from polyacrylonitrile and copolymer of methylmethacrylate‐dichlorophenylmaleimide

Two new ultrafiltration membranes were obtained from a polymer mixture, containing 60% polyacrylonitrile (PAN) and 40% copolymer of methylmethacrylate‐dichlorophenylmaleimide (MMA‐DCPMI). Membrane 1 (MB1) contains 40% DCPMI of the copolymer, and membrane 2 (MB2) contains 15% of the copolymer. The pore size, the specific surface, the water content, the water flux, and the selectivity were determined for the two membranes. The presence of dichlorophenylmaleimide in the copolymer ensures the preparation of membranes suitable for direct covalent enzyme immobilization without further modifications. These membranes were used for immobilization of glucose oxidase (GOD). High amount of bound protein was found on each of the membranes. High relative activities of the immobilized GOD were achieved, 72% for MB1 and 68% for MB2. The properties of the immobilized enzyme (GOD) were determined: optimum pH and temperature and pH, thermal, and storage stability, and then compared with the properties of the native enzyme. The kinetic parameters of the enzyme reaction, Michaelis constant (K_m) and maximum reaction rate (V_max), were also investigated. The results obtained showed that the ultrafiltration membranes prepared from the mixture of PAN and the copolymer MMA‐DCPMI were suitable for use as carriers for the immobilization of GOD. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4334–4340, 2006     

Simultaneous covalent immobilization of glucose oxidase and catalase onto chemically modified acrylonitrile copolymer membranes

Ultrafiltration membranes from acrylonitrile copolymer were chemically modified with different concentrations of hydrogen peroxide (from 5 to 30% H₂O₂). The amount of the amide groups in the modified membranes was determined. The water flow and permeability coefficients of the initial and modified membranes were also researched. The modified membranes were used as carriers for covalent immobilization of the dual enzyme system of glucose oxidase and catalase (GOD+CAT). It was found that the best matrices for immobilization of the dual system were membranes modified with 20% H₂O₂ and the optimal activity ratio was GOD : CAT = 1 : 5. The glucose conversion efficiency with the dual enzyme system was twice as high as that of bound GOD alone. Some of the basic characteristics (optimum pH, optimum temperature, pH, temperature stability, and storage stability) of the dual enzyme system were determined and compared with characteristics of free and bound enzymes. The catalytic parameters of the enzyme reaction (K_m and V_max) were determined with GOD immobilized alone and with the dual system GOD+CAT. The higher rate observed with the dual enzyme system clearly showed the advantage and the efficiency of the immobilized system. Glucose oxidase without catalase was deactivated by H₂O₂ more rapidly than the immobilized dual GOD+CAT system. These experimental evidences can be explained by the protecting effect of catalase on glucose oxidase from inhibition by H₂O₂. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4057–4063, 2004     

Chitosan‐grafted poly(hydroxyethyl methacrylate‐co‐glycidyl methacrylate) membranes for reversible enzyme immobilization

Epoxy group‐containing poly(hydroxyethyl methacrylate/glycidyl methacrylate), p(HEMA/GMA), membrane was prepared by UV initiated photopolymerization. The membrane was grafted with chitosan (CH) and some of them were chelated with Fe(III) ions. The CH grafted, p(HEMA/GMA), and Fe(III) ions incorporated p(HEMA/GMA)‐CH‐Fe(III) membranes were used for glucose oxidase (GOD) immobilization via adsorption. The maximum enzyme immobilization capacity of the p(HEMA/GMA)‐CH and p(HEMA/GMA)‐CH‐Fe(III) membranes were 0.89 and 1.36 mg/mL, respectively. The optimal pH value for the immobilized GOD preparations is found to have shifted 0.5 units to more acidic pH 5.0. Optimum temperature for both immobilized preparations was 10°C higher than that of the free enzyme and was significantly broader at higher temperatures. The apparent K_m values were found to be 6.9 and 5.8 mM for the adsorbed GOD on p(HEMA/GMA)‐CH and p(HEMA/GMA)‐CH‐Fe(III) membranes, respectively. In addition, all the membranes surfaces were characterized by contact angle measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3084–3093, 2007     

Preparation and characterization of a poly(vinyl alcohol)/tetraethoxysilane ultrafiltration membrane by a sol–gel method

Using poly(vinyl alcohol) (PVA) with highly hydrophilic properties as membrane material and poly(ethylene glycol) (PEG) as an additive, we prepared PVA/tetraethoxysilane (TEOS) ultrafiltration (UF) membranes with good antifouling properties by a sol–gel method. The PVA/TEOS UF membranes were characterized by X‐ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron microscopy, and static contact angle of measurement of water. The hybridization of TEOS to PVA for preparing the PVA/TEOS UF membranes achieved the required permeation performance and good antifouling behaviors. The morphology and permeation performance of the PVA/TEOS membranes varied with the different TEOS loadings and PEG contents. The pure water fluxes (J_W) increased and the rejections (Rs) decreased with increasing TEOS loading and PEG content. The PVA/TEOS UF membrane with a PVA/TEOS/PEG/H₂O composition mass ratio of 10/3/4/83 in the dope solution had a J_W of 66.5 L m^?2 h^?1 and an R of 60.3% when we filtered it with 300 ppm of bovine serum albumin aqueous solution at an operational pressure difference of 0.1 MPa. In addition, the filtration and backwashing experiment proved that the PVA/TEOS membranes possessed good long‐term antifouling abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4066–4074, 2013     

Preparation of Cu(II)‐chelated poly(vinyl alcohol) nanofibrous membranes for catalase immobilization

Poly(vinyl alcohol) (PVA) nanofibers were formed by electrospinning. Metal chelated nanofibrous membranes were prepared by reaction between Cu(II) solution and nanofibers, and which were used as the matrix for catalases immobilization. The constants of Cu(II) adsorption and properties of immobilized catalases were studied in this work. The Cu(II) concentration was determined by atomic absorption spectrophotometer (AAS), the immobilized enzymes were confirmed by the Fourier transform infrared spectroscopy (FTIR), and the amounts of immobilized enzymes were determined by the method of Bradford on an ultraviolet spectrophotometer (UV). Adsorption of Cu(II) onto PVA nanofibers was studied by the Langmuir isothermal adsorption model. The maximum amount of coordinated Cu(II) (q_m) was 2.1 mmol g⁻¹ (dry fiber), and the binding constant (K_l) was 0.1166 L mmol⁻¹. The immobilized catalases showed better resistance to pH and temperature inactivation than that of free form, and the thermal and storage stabilities of immobilized catalases were higher than that of free catalases. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (8425.8 μmol mg⁻¹) for the immobilized catalases was smaller than that of the free catalases (10153.6 μmol mg⁻¹), while the K_m for the immobilized catalases were larger. It was also found that the immobilized catalases had a high affinity with substrate, which demonstrated that the potential of PVA‐Cu(II) chelated nanofibrous membranes applied to enzyme immobilization and biosensors. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Immobilization of carbonic anhydrase on polyethylenimine/dopamine codeposited membranes

Carbonic anhydrase (CA) catalyzing CO₂ hydration has an important application in carbon capture, and its immobilization is very significant. Here, CA was covalently linked by glutaraldehyde (GA) to the surface of poly(vinylidene fluoride) (PVDF) and polyethylene (PE) membranes, which were previously modified via a simple codeposition of polyethyleneimine (PEI) and dopamine (DA). The effects of the modification conditions were investigated, and the membranes were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The immobilization process was optimized, and the catalytic properties of immobilized CA were studied. The results show that the optimal mass ratio of PEI and DA was 1:1 and the deposition time was 10–12 h, at which the surface amino group density could reach 1.278 × 10⁻⁷ and 1.397 × 10⁻⁷ mol/cm² for PVDF and PE, respectively. For enzyme immobilization, the optimal CA and GA concentrations were 0.2 mg/mL and 0.1 wt %, and a maximum activity recovery of about 53% and 76% could be achieved for PVDF-attached CA and PE-attached CA, respectively. Their K_m values were 10.62 mM and 8.6 mM, and the corresponding K_cat/K_m values were 132.2 M⁻¹ s⁻¹ and 312.9 M⁻¹ s⁻¹. After immobilization, the storage stability and reusability of CA were much improved. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47784.     

Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

Organic–inorganic hybrid materials. II. Chain mobility and stability of polysiloxaneimide–silica hybrids

Polysiloxaneimide–silica hybrid materials (PSI‐SiO₂) were obtained using the sol–gel technique by polycondensation of tetramethoxysilane (TMOS) in a polyamic acid solution. IR, ²⁹Si‐ and ¹³C‐NMR spectroscopy, and thermogravimetric analysis were used to study hybrids containing various proportions of TMOS and hydrolysis ratios. The morphology, dynamics, and thermal stability of the hybrids were investigated. The chain mobility of the hybrids was investigated by spin–spin relaxation time (T₂) measurements. The apparent activation energy (E_a) for degradation of the hybrids in air was studied by the van Krevelen method. The T₂ value was independent of the silica content whereas that of the E_a decreased as silica content increased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 965–973, 2001     

Palygorskite-poly(o-phenylenediamine) nanocomposite: An enhanced electrochemical platform for glucose biosensing

Palygorskite (Pal) may be a promising material for enzyme immobilization due to its large surface, high biocompatibility and stability. This attractive material combined with a conducting polymer, poly(o-phenylenediamine), was exploited as a platform for the immobilization of glucose oxidase (GOD) using glutaraldehyde as crosslinker, and thus a novel glucose biosensor was obtained. The results of electrochemical impedance spectroscopy (EIS) and SEM indicated the successful entrapment of GOD in the clay polymer nanocomposite (CPN) film. Amperometric detection of glucose was performed by holding the potential at the CPN electrode at 0.6 V for the oxidation of H₂O₂ generated in the enzymatic reaction. The apparent Michaelis–Menten constant (K_M^app) was calculated to be 5.25 mM, which is close to that of the free enzyme. The proposed biosensor exhibited a wide linear range, a low detection limit, a good reproducibility and accepted stability in the determination of glucose, providing a biocompatible platform for glucose biosensing.     

Covalent immobilization of trypsin onto thermo‐sensitive poly(N‐isopropylacrylamide‐co‐acrylic acid) microspheres with high activity and stability

Poly(N‐isopropylacrylamide‐co‐acrylic acid) (P(NIPAM‐co‐AA)) microspheres with a high copolymerized AA content were fabricated using rapid membrane emulsification technique. The uniform size, good hydrophilicity, and thermo sensitivity of the microspheres were favorable for trypsin immobilization. Trypsin molecules were immobilized onto the microspheres surfaces by covalent attachment. The effects of various parameters such as immobilization pH value, enzyme concentration, concentration of buffer solution, and immobilization time on protein loading amount and enzyme activity were systematically investigated. Under the optimum conditions, the protein loading was 493 ± 20 mg g^?1 and the activity yield of immobilized trypsin was 155% ± 3%. The maximum activity (V_max) and Michaelis constant (K_m) of immobilized enzyme were found to be 0.74 μM s^?1 and 0.54 mM, respectively. The immobilized trypsin showed better thermal and storage stability than the free trypsin. The enzyme‐immobilized microspheres with high protein loading amount still can show a thermo reversible phase transition behavior. The research could provide a strategy to immobilize enzyme for application in proteomics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43343.     

A simple method for biocatalyst immobilization using PVA‐based hydrogel particles

BACKGROUND: The aim of this study was to evaluate the feasibility of enzyme immobilization in PVA particles through extrusion of LentiKat^®Liquid in polyethylene glycol. Inulinase, with invertase activity for sucrose hydrolysis, was used as model system. RESULTS: Inulinase was effectively immobilized in PVA particles. The pH optimum of the enzyme activity was broadened for lower pH values. Mechanical instability of the PVA under prolonged incubation above 55 °C was observed. A 1.8‐fold increase in the apparent K_M (Michaelis constant) suggests diffusion limitations as a result of immobilization. The immobilized biocatalyst exhibited considerable operational stability, since a decrease of roughly 10% in the product yield after 24 h biotransformation runs was observed in trials performed at 50 °C, following 20 repeated, consecutive batches. CONCLUSION: The results obtained highlight the potential of PVA‐based particles obtained through extrusion into PEG for the production of suitable biocatalysts for application in large‐scale processes. Copyright © 2008 Society of Chemical Industry     

Novel anion‐exchange organic‐inorganic hybrid membranes prepared through sol‐gel reaction and UV/thermal curing

Anion‐exchange organic‐inorganic hybrid membranes were prepared through sol‐gel reaction and UV/thermal curing of positively charged alkoxysilane and the alkoxysilane containing acrylate or epoxy groups. Properties of prepared hybrid membranes were varied by control of the molar ratio of the precursors. It was shown that the thermal degradation temperatures (T_d) of the membranes were in the range of 212–226°C, water uptakes in the range of 9.6–14.6% and IEC values in the range of 0.9–1.6 mmol g^?1. The hybrid membranes show high permeability to anions, as reflected by the high static transport number (t_?) of the anion (Cl^?). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

In situ sol–gel route to novel sulfonated polyimide?SiO2 hybrid proton‐exchange membranes for direct methanol fuel cells

Polyimides (PIs) as high‐performance organic matrices are used in the preparation of PI composites because of their excellent mechanical, thermal and dielectric properties. The sol–gel method is a promising technique for preparing these PI composites due to the mild reaction conditions and the process being controllable. Although sulfonated polyimide (SPI) proton‐exchange membranes have attracted much attention recently, studies on preparing SPI‐based hybrid proton‐exchange membranes for fuel cells have been rare. A series of SPI? SiO₂ hybrid proton‐exchange membranes were prepared from amino‐terminated SPI pre‐polymers, 3‐glycidoxypropyltrimethoxysilane (KH‐560) and tetraethylorthosilicate through a co‐hydrolysis and condensation process using an in situ sol–gel method. The reactive silane KH‐560 was used to react with amino‐terminated SPI to form silane‐capped SPI in order to improve the compatibility between the polymer matrix and the inorganic SiO₂ phase. The microstructure and mechanical, thermal and proton conduction properties were studied in detail. The hybrid membranes were highly uniform without phase separation up to 30 wt% SiO₂. The storage modulus and tensile strength of the hybrid membranes increased with increasing SiO₂ content. The introduction of SiO₂ improved the methanol resistance while retaining good proton conductivity. The hybrid membrane with 30 wt% SiO₂ exhibited a proton conductivity of 10.57 mS cm^?1 at 80 °C and methanol permeability of 2.3 × 10^?6 cm² s^?1 possibly because the crosslinking structure and SiO₂ phases formed in the hybrids could retain water and were helpful to proton transport. Copyright © 2010 Society of Chemical Industry     

Immobilization of invertase onto dimer acid‐co‐alkyl polyamine

Invertase was immobilized onto the dimer acid‐co‐alkyl polyamine after activation with 1,2‐diamine ethane and 1,3‐diamine propane. The effects of pH, temperature, substrate concentration, and storage stability on free and immobilized invertase were investigated. Kinetic parameters were calculated as 18.2 mM for K_m and 6.43 × 10^?5 mol dm^?3 min^?1 for V_max of free enzyme and in the range of 23.8–35.3 mM for K_m and 7.97–11.71 × 10^?5 mol dm^?3 min^?1 for V_max of immobilized enzyme. After storage at 4°C for 1 month, the enzyme activities were 21.0 and 60.0–70.0% of the initial activity for free and immobilized enzyme, respectively. The optimum pH values for free and immobilized enzymes were determined as 4.5. The optimum temperatures for free and immobilized enzymes were 45 and 50°C, respectively. After using immobilized enzyme in 3 days for 43 times, it showed 76–80% of its original activity. As a result of immobilization, thermal and storage stabilities were increased. The aim of this study was to increase the storage stability and reuse number of the immobilized enzyme and also to compare this immobilization method with others with respect to storage stability and reuse number. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1526–1530, 2004     

Branched Polyvinyl Alcohol Hybrid Membrane for Acid Recovery via Diffusion Dialysis

A branched polymer was prepared by grafting allyltrimethylammonium chloride onto polyvinyl alcohol (PVA) via free‐radical polymerization. Afterwards, a series of hybrid membranes were prepared by sol‐gel cross‐linking between quaternary ammonium‐PVA and tetraethoxysilane. The obtained membranes were characterized in terms of infrared spectroscopy, ion exchange capacity, water uptake, linear expansion ratio, and acid resistance. The thermal properties of the membranes were investigated as well. The diffusion dialysis performances of the membranes were tested by using a simulated feed solution containing HCl and FeCl₂. The diffusion dialysis coefficients and the separation factors were much better than those of the commercial DF‐120 membrane.     

Cryostructuring of polymer systems. XXVI. Heterophase organic–inorganic cryogels prepared via freezing–thawing of aqueous solutions of poly(vinyl alcohol) with added tetramethoxysilane

Composite heterophase organic–inorganic hybrid cryogels of poly(vinyl alcohol) (PVA) containing silica constituents were prepared and studied. Such constituents were formed in the course of hydrolytic polycondensation (sol‐gel process) of tetramethoxysilane (TMOS) introduced in to the aqueous polymer solution prior to its freeze–thaw treatment. It was shown that moderate (over the range of ?15 to ?30°C) freezing, then frozen storage, and subsequent thawing of the water/PVA/TMOS systems resulted in the formation of macroporous composite cryogels filled with dispersed silica particles (discrete phase). The continuous phase of such gel materials represents the supramolecular PVA network, which is supposed to be additionally cured with the silicon‐containing oligomeric cross agents formed from TMOS in the course of hydrolytic polycondensation. The incorporated silica components influenced the morphology of cryogels. The effects of significant increase in gel strength and heat resistance with increasing TMOS concentration in the initial feed and with thawing rate decreasing have also been observed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Immobilization of β-galactosidase onto polymeric supports

Poly(vinyl alcohol) cross-linked with para-formaldehyde (PVA–F) and natural polysaccharide–chitosan in bead form and salicylic acid–resorcinol–formaldehyde polymeric resin (SRF) in powder form were used for immobilization of β-galactosidase through covalent linkages. Various activation processes and conditions were optimized. Immobilized enzyme showed very good storage stability at room temperature. Durability of the enzyme was also improved on immobilization. On repeated use of enzyme immobilized on chitosan beads, no loss was observed in enzyme activity even after 10 batches. Michaelis constant K_m and maximum reaction velocity V_m were calculated for free and immobilized enzyme systems. Effect of pH and temperature on enzyme activity was estimated and energy of activation (E_a) and inactivation constant (K_i) for free and immobilized enzyme were calculated. © 1995 John Wiley & Sons, Inc.     

Lipase immobilized on poly (vinyl alcohol) modified polysulfone membrane: application in hydrolytic activities for olive oil

The advancement of membrane research closely relates to the activities of ‘immobilization of enzymes’. The modification of polymeric membrane surfaces according to tailor-made specifications is considered an art and useful in this arena. In this study, lipase is immobilized on Polyvinyl alcohol photomodified Polysulfone (PS–PVA) membranes. The maximum immobilization (1.48 mg/cm²) for PS–PVA membranes is achieved. The amount of immobilized lipase directly relates on the PVA content on the membrane. Scanning Electron Microscope and X-ray diffraction patterns show the evidences of lipase immobilization on membranes. The hydrolytic performances of lipase immobilized PS and PS–PVA–glu membranes for olive oil are studied. The free fatty acid (FFA %) and acid value (AV) parameters are determined by titrimetic analysis (1.53 and 3.04 for PS–PVA–glu) and compared with esterification GC-mass analysis data. The K _m and V _max values are 105 mM and 0.9 mM/min for lipase immobilized on PS–PVA–glu and 153.8 mM and 0.51 mM/min for lipase on PS. The reusability feature shows the lipase immobilized on PS–PVA–glu matrix have better stability (10.7% decrease) compared to lipase immobilized on PS matrix (33.3% decrease) after five cycles.     

Towards the design of non-amyloidogenic proteins

Glucose oxidase was immobilized onto poly(2-hydroxyethyl methacrylate) (pHEMA) membranes by two methods: by covalent bonding through epichlorohydrin and by entrapment between pHEMA membranes. The highest immobilization efficiency was found to be 17.4% and 93.7% for the covalent bonding and entrapment, respectively. The K_m values were 5.9 mmol dm^?3, 8.8 mmol dm^?3 and 12.4 mmol dm^?3 for free, bound and entrapped enzyme, respectively. The V_max values were 0.071 mmol dm^?3 min^?1, 0.067 mmol dm^?3 min^?1 and 0.056 mmol dm^?3 min^?1 for free, bound and entrapped enzyme. When the medium was saturated with oxygen, K_m was not significantly altered but V_max was. The optimum pH values for the free, covalently-bound and entrapped enzyme were determined to be 5, 6, and 7, respectively. The optimum temperature was 30°C for free or covalently-bound enzyme but 35°C for entrapped enzyme. The deactivation constant for bound enzyme was determined as 1.7 × 10^?4 min^?1 and 6.9 × 10^?4 min^?1 for the entrapped enzyme.     

6FDA-TAPOB hyperbranched polyimide-silica hybrids for gas separation membranes

Physical and gas transport properties of hyperbranched polyimide-silica hybrid membranes were investigated. Hyperbranched polyamic acid as a precursor was prepared by polycondensation of a triamine, 1,3,5-tris(4-aminophenoxy) benzene (TAPOB), and a dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and subsequently modified a part of end groups by 3-aminopropyltrimethoxysilane (APTrMOS). The hyperbranched polyimide-silica hybrid membranes were prepared by sol–gel reaction using the polyamic acid, water, and alkoxysilanes. 5% weight-loss temperature of the hybrid membranes increased with increasing silica content, indicating effective crosslinking at polymer-silica interface mediated by APTrMOS moiety. On the other hand, glass transition temperature of the hybrid membranes prepared with methyltrimethoxysilane (MTMS) showed a minimum value at low silica content region, suggesting insufficient formation of three-dimensional Si O Si network compared to the hybrid membranes prepared with tetramethoxysilane (TMOS). CO₂, O₂, N₂, and CH₄ permeability coefficients of the hybrid membranes increased with increasing silica content. Especially for TMOS/MTMS combined system, the hybrid membranes showed simultaneous enhancements of gas permeability and CO₂/CH₄ separation ability. It was concluded that the 6FDA-TAPOB hyperbranched polyimide-silica hybrid membranes have high thermal stability and excellent CO₂/CH₄ selectivity and are expected to apply to high-performance gas separation membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008