Porous dye affinity beads for albumin separation from human plasma

Porous polymeric beads were obtained by the suspension polymerization of 2‐hydroxyethyl methacrylate (HEMA) and ethylene glycol dimethacrylate (EGDMA). Poly(HEMA–EGDMA) beads were characterized by surfacearea measurements, swelling studies, FTIR, scanning electron microscopy (SEM), and elemental analysis. Poly (HEMA–EGDMA) beads had a specific surface area of 56 m²/g. SEM observations showed that the poly(HEMA–EGDMA) beads abounded macropores. Poly(HEMA–EGDMA) beads with a swelling ratio of 55%, and containing different amounts of Reactive Red 120 (9.2–39.8 μmol/g) were used in the adsorption/desorption of human serum albumin (HSA) from aqueous solutions and human plasma. The nonspecific adsorption of HSA was very low (0.2 mg/g). The maximum HSA adsorption amount from aqueous solution in phosphate buffer was 60.1 mg/g at pH 5.0. Higher HSA adsorption value was obtained from human plasma (up to 95.7 mg/g) with a purity of 88%. The equilibrium monolayer adsorption amount, Q_max was determined as 172.4 mg/g. The dimensionless separation factor (R_L) value shows that the adsorption behavior of HSA onto the Reactive Red 120 attached poly(HEMA–EGDMA) beads was favorable (0 < R_L < 1). Desorption of HSA from Reactive Red 120 attached poly (HEMA–EGDMA) beads was performed using 0.1M Tris/HCl buffer containing 0.5M NaCl. It was observed that HSA could be repeatedly adsorbed and desorbed with Reactive Red 120‐attached poly(HEMA–EGDMA) beads without significant loss in the adsorption amount. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Alanine containing porous beads for mercury removal from artificial solutions

N‐methacryloyl‐(L )‐alanine (MALA) was synthesized by using methacryloyl chloride and alanine as a metal‐complexing ligand or comonomer. Spherical beads with an average diameter of 150–200 μm were obtained by suspension polymerization of MALA and 2‐hydroxyethyl methacrylate (HEMA) conducted in an aqueous dispersion medium. Poly(HEMA–MALA) beads were characterized by SEM, swelling studies, surface area measurement, and elemental analysis. Poly(HEMA–MALA) beads have a specific surface area of 68.5 m²/g. Poly(HEMA–MALA) beads with a swelling ratio of 63%, and containing 247 μmol MALA/g were used in the removal of Hg²⁺ from aqueous solutions. Adsorption equilibrium was achieved in about 60 min. The adsorption of Hg²⁺ ions onto PHEMA beads was negligible (0.3 mg/g). The MALA incorporation into the polymer structure significantly increased the mercury adsorption capacity (168 mg/g). Adsorption capacity of MALA containing beads increased significantly with pH. The adsorption of Hg²⁺ ions increased with increasing pH and reached a plateau value at around pH 5.0. Competitive heavy metal adsorption from aqueous solutions containing Cd²⁺, Cu²⁺, Pb²⁺, and Hg²⁺ was also investigated. The adsorption capacities are 44.5 mg/g for Hg²⁺, 6.4 mg/g for Cd²⁺, 2.9 mg/g for Pb²⁺, and 2.0 mg/g for Cu²⁺ ions. These results may be considered as an indication of higher specificity of the poly(HEMA–MALA) beads for the Hg²⁺ comparing to other ions. Consecutive adsorption and elution operations showed the feasibility of repeated use for poly(HEMA–MALA) chelating beads. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1222–1228, 2006     

Adsorption of Ni2+ from aqueous solutions by novel polyethyleneimine‐attached poly(p‐chloromethylstyrene) beads

In this study Ni²⁺ adsorption properties of polyethyleneimine (PEI)‐attached poly(p‐chloromethylstyrene) (PCMS) beads were investigated. Spherical beads with an average size of 186 μm were obtained by the suspension polymerization of p‐chloromethylstyrene conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, PCMS beads had a specific surface area of 14.1 m²/g. PEI chains could be covalently attached onto the PCMS beads with equilibrium binding capacities up to 208 mg PEI/g beads, via a direct chemical reaction between the amine and chloro‐methyl groups. After PEI adsorption with 10% (w/w) initial PEI concentration, free amino content of PEI‐attached PCMS beads was determined as 0.91 mEq/g. PEI‐attached PCMS beads were utilized as adsorbents in the adsorption/desorption of Ni²⁺ ions from synthetic solutions. The adsorption process was fast; 90% of adsorption occurred within 90 min, and equilibrium was reached at around 2 h. Adsorption capacity was obtained to be 78.2 mg/g at a pH of about 6.0. The chelating beads can be easily regenerated by 0.1 M HNO₃ with higher effectiveness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2467–2473, 2002     

Reactive red 120 and NI(II) derived poly(2‐hydroxyethyl methacrylate) nanoparticles for urease adsorption

Non‐porous poly(2‐hydroxyethyl methacrylate) [p(HEMA)] nanoparticles were prepared by surfactant free emulsion polymerization. The p(HEMA) nanoparticles was about 200 nm diameter, spherical form, and non‐porous. Reactive Red 120 (RR 120) was covalently attached to the p(HEMA) nanoparticles and Ni(II) ions were incorporated to attach dye molecules. Urease was immobilized onto RR120‐Ni(II) attached p(HEMA) nanoparticles via adsorption. The maximum urease adsorption capacity of RR120‐Ni(II) attached p(HEMA) nanoparticles was 480.01 mg g^?1 nanoparticles at pH 7.0 in phosphate buffer. It was observed that urease could be repeatedly adsorbed and desorbed without significant loss in adsorption amount. K_m values were 21.50 and 34.06 mM for the free and adsorbed enzyme. The V_max values were 4 U for the free enzyme and 3.3 U for the adsorbed enzyme. The optimum pH was 25 mM pH 7 phosphate buffer for free and adsorbed enzyme. The optimum temperature was determined at 35°C and 55°C for the free and adsorbed enzyme, respectively. These findings show considerable promise for this material as an adsorption matrix in biotechnological applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39757.     

Methacryloylamidoglutamic acid functionalized poly(2-hydroxyethyl methacrylate) beads for UO22+ removal

A novel approach was developed to obtaining high uranium adsorption capacity utilizing 2-methacryloylamidoglutamic acid (MAGA) as a metal-complexing ligand. MAGA was synthesized by using methacryloyl chloride and glutamic acid. Spherical beads with an average size of 150–200 μm were obtained by suspension polymerization of MAGA and 2-hydroxyethyl methacrylate (HEMA) conducted in an aqueous dispersion medium. Poly(2-hydroxyethyl methacrylate–methacryloylamidoglutamic acid) [p(HEMA–MAGA)] beads have a specific surface area of 56.7 m²/g. p(HEMA–MAGA) beads were characterized by swelling studies, FTIR and elemental analysis. The p(HEMA–MAGA) beads with a swelling ratio of 63%, and containing 3.5 mmol MAGA/g were used in the removal of UO₂²⁺ from aqueous solutions. Adsorption equilibrium was achieved in about 120 min. The adsorption of uranium(VI) ions onto pHEMA was negligible (1.4 mg/g). The MAGA incorporation significantly increased the uranium adsorption capacity (204.8 mg/g). Adsorption capacity of MAGA incorporated beads increased significantly with pH and then reached the maximum at pH 6.0. Consecutive adsorption and elution operations showed the feasibility of repeated use for p(HEMA–MAGA) chelating beads.     

Preparation and Characterization of the Newly Synthesized Metal‐Complexing‐Ligand N‐Methacryloylhistidine Having PHEMA Beads for Heavy Metal Removal from Aqueous Solutions

The aim of this study was to investigate in detail the performance for removal of heavy metal ions of beads composed of poly(2‐hydroxyethyl methacrylate) (pHEMA) to which N‐methacryloylhistidine (MAH) was copolymerized. The metal‐complexing ligand MAH was synthesized by using methacryloyl chloride and histidine. Spherical beads with an average size of 150–200 μm were obtained by the radical suspension polymerization of MAH and HEMA conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, p(HEMA‐MAH) beads had a specific surface area of 17.6 m²/g. The synthesized MAH monomer was characterized by NMR; p(HEMA‐MAH) beads were characterized by swelling studies, FTIR and elemental analysis. The p(HEMA‐MAH) beads with a swelling ratio of 65%, and containing 1.6 mmol MAH/g, were used in the adsorption/desorption experiments. Adsorption capacity of the beads for the selected metal ions, i. e., Cu(II), Cd(II), Cr(III), Hg(II) and Pb(II), were investigated in aqueous media containing different amounts of these ions (10–750 mg/L) and at different pH values (3.0–7.0). Adsorption equilibria were established in about 20 min. The maximum adsorption capacities of the p(HEMA‐MAH) beads were 122.7 mg/g for Cu(II), 468.8 mg/g for Cr(III), 639.4 mg/g for Cd(II), 714.1 mg/g for Pb(II) and 1 234.4 mg/g for Hg(II). pH significantly affected the adsorption capacity of MAH incorporated beads. The chelating beads can be easily regenerated by 0.1 M HNO₃ with high effectiveness. These features make p(HEMA‐MAH) beads a potential candidate for heavy metal removal at high capacity.     

Congo red attached poly(EGDMA–HEMA) microspheres as specific sorbents for removal of cadmium ions

Poly[ethyleneglycoldimethacrylate (EGDMA)–hydroxyethylmethacrylate (HEMA)] microspheres (150–200 μm in diameter) were produced by suspension copolymerization of EGDMA and HEMA in an aqueous medium. Toluene was included in the formulations in order to produce water-swellable microspheres. Poly(vinyl alcohol) and benzoyl peroxide were used as stabilizer and initiator, respectively. Congo red was chemically attached to the microspheres as a metal chelating ligand for specific adsorption of heavy metal ions. These sorbents were characterized by an optical microscopy and a FTIR. Adsorption/desorption of cadmium (Cd²⁺) ions from aqueous solutions on these sorbents were investigated in batch equilibrium experiments by using an atomic absorption spectroscopy with a graphite furnace atomizer. The maximum cadmium adsorption on to the dye-attached microspheres (i.e., by complex formation) was about 18.3 mg Cd²⁺ ions/g polymer, which was observed at pH 6.8. While adsorption onto the plain poly(EGDMA–HEMA) microspheres (i.e., nonspecific adsorption) was about 0.93 mg Cd²⁺ ions/g polymer at the same conditions. More than 90% of the adsorbed cadmium was desorbed in 1 h by using 2M NaCl as an eluant. The resorption capacity of the sorbent did not significantly decrease during repeated sorption–desorption cycling. © 1996 John Wiley & Sons, Inc.     

Preparation of Zn2+‐chelated poly(HEMA‐MAH) cryogel for affinity purification of chicken egg lysozyme

Supermacroporous poly(2‐hydroxyethyl methacrylate) [poly(HEMA)]‐based monolithic cryogel column was prepared by radical cryocopolymerization of HEMA with N‐methacryloyl‐L ‐histidine methyl ester (MAH) as functional comonomer and N,N′‐methylene‐bisacrylamide (MBAAm) as crosslinker directly in a plastic syringe for affinity purification of lysozyme from chicken egg white. The monolithic cryogel containing a continuous polymeric matrix having interconnected pores of 10–50 μm size was loaded with Zn²⁺ ions to form the metal chelate with poly(HEMA‐MAH) cryogel. Poly(HEMA‐MAH) cryogel was characterized by swelling studies, FTIR, scanning electron microscopy, and elemental analysis. The equilibrium swelling degree of the poly(HEMA‐MAH) monolithic cryogel was 5.62 g H₂O/g cryogel. Poly(HEMA‐MAH) cryogel containing 45.8 μmol MAH/g was used in the adsorption/desorption of lysozyme from aqueous solutions. The nonspecific adsorption of lysozyme was very low (7.5 mg/g). The maximum amount of lysozyme adsorption from aqueous solution in phosphate buffer was 209 mg/g at pH 7.0. It was observed that lysozyme could be repeatedly adsorbed and desorbed with the poly(HEMA‐MAH) cyogel without significant loss of adsorption capacity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ion imprinted beads embedded cryogels for in vitro removal of iron from β-thalassemic human plasma

Molecular recognition based Fe³⁺ imprinted poly(GMA-MAC) (MIP) beads embedded PHEMA composite cryogel was prepared for selective removal of Fe³⁺ ions from β-thalassemia patient plasma. The precomplexation was achieved by the coordination of Fe³⁺ ions with N-methacryloyl-(L )-cysteine methyl ester (MAC-Fe³⁺). MIP beads were prepared by dispersion polymerization in the presence of MAC-Fe³⁺ complex and glycidyl methacrylate (GMA) monomer. Then the MIP beads were embedded into poly(hydroxyethyl methacrylate) (PHEMA) cryogel. The specific surface area and the swelling degree of the PHEMA-MIP composite cryogel were found to be 76.8 m²/g and 7.7 g H₂O/g cryogel, respectively. The maximum adsorption amount of Fe³⁺ ions was 2.23 mg/g. The relative selectivity of PHEMA-MIP composite cryogel towards the Fe³⁺ ions was 135.0, 61.4, and 57.0 times greater than that of the PHEMA-NIP cryogel as compared with the Ni²⁺, Zn²⁺, and Fe²⁺ ions, respectively. PHEMA-MIP composite cryogel was recovered and reused many times without any significant decrease in its adsorption capacity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Metal‐chelating properties of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) membranes

Metal‐chelating membranes have advantages as adsorbents in comparison with conventional beads because they are not compressible and they eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) [poly(HEMA–MAH)] membranes for the removal of three toxic heavy‐metal ions—Cd(II), Pb(II), and Hg(II)—from aquatic systems. The poly(HEMA–MAH) membranes were characterized with scanning electron microscopy and ¹H‐NMR spectroscopy. The adsorption capacity of the poly(HEMA–MAH) membranes for the selected heavy‐metal ions from aqueous media containing different amounts of these ions (30–500 mg/L) and at different pH values (3.0–7.0) was investigated. The adsorption capacity of the membranes increased with time during the first 60 min and then leveled off toward the equilibrium adsorption. The maximum amounts of the heavy‐metal ions adsorbed were 8.2, 31.5, and 23.2 mg/g for Cd(II), Pb(II), and Hg(II), respectively. The competitive adsorption of the metal ions was also studied. When the metal ions competed, the adsorbed amounts were 2.9 mg of Cd(II)/g, 14.8 mg of Pb(II)/g, and 9.4 mg of Hg(II)/g. The poly(HEMA–MAH) membranes could be regenerated via washing with a solution of nitric acid (0.01M). The desorption ratio was as high as 97%. These membranes were suitable for repeated use for more than three adsorption/desorption cycles with negligible loss in the adsorption capacity. The stability constants for the metal‐ion/2‐methacryloylamidohistidine complexes were calculated to be 3.47 × 10⁶, 7.75 × 10⁷, and 2.01 × 10⁷ L/mol for Cd(II), Pb(II), and Hg(II) ions, respectively, with the Ruzic method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1213–1219, 2005     

Nickel(II)‐imprinted monolithic columns for selective nickel recognition

Ni²⁺‐imprinted monolithic column was prepared for the removal of nickel ions from aqueous solutions. N‐Methacryloyl‐L ‐histidine was used as a complexing monomer for Ni²⁺ ions in the preparation of the Ni²⁺‐imprinted monolithic column. The Ni²⁺‐imprinted poly(hydroxyethyl methacrylate‐N‐methacryloyl‐L ‐histidine) (PHEMAH) monolithic column was synthesized by bulk polymerization. The template ion (Ni²⁺) was removed with a 4‐(2‐pyridylazo) resorcinol (PAR):NH₃? NH₄Cl solution. The water‐uptake ratio of the PHEMAH–Ni²⁺ monolith increased compared with PHEMAH because of the formation of nickel‐ion cavities in the polymer structure. The adsorption of Ni²⁺ ions on both the PHEMAH–Ni²⁺ and PHEMAH monoliths were studied. The maximum adsorption capacity was 0.211 mg/g for the PHEMAH–Ni²⁺ monolith. Fe³⁺, Cu²⁺, and Zn²⁺ ions were used as competitive species in the selectivity experiments. The PHEMAH–Ni²⁺ monolithic column was 268.8, 25.5, and 10.4 times more selective than the PHEMAH monolithic column for the Zn²⁺, Cu²⁺, and Fe³⁺ ions, respectively. The PHEMAH–Ni²⁺ monolithic column could be used repeatedly without a decrease in the Ni²⁺ adsorption capacity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Removal of heavy‐metal ions by magnetic beads containing triazole chelating groups

The aim of this study was to prepare magnetic beads that could be used for the removal of heavy‐metal ions from synthetic solutions. Magnetic poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [m‐poly(EGDMA–VTAZ)] beads were produced by suspension polymerization in the presence of a magnetite Fe₃O₄ nanopowder. The specific surface area of the m‐poly(EGDMA–VTAZ) beads was 74.8 m²/g with a diameter range of 150–200 μm, and the swelling ratio was 84%. The average Fe₃O₄ content of the resulting m‐poly(EGDMA–VTAZ) beads was 14.8%. The maximum binding capacities of the m‐poly(EGDMA–VTAZ) beads from aquous solution were 284.3 mg/g for Hg²⁺, 193.8 mg/g for Pb²⁺, 151.5 mg/g for Cu²⁺, 128.1 mg/g for Cd²⁺, and 99.4 mg/g for Zn²⁺. The affinity order on a mass basis was Hg²⁺ > Pb²⁺ > Cu²⁺ > Cd²⁺> Zn²⁺. The binding capacities from synthetic waste water were 178.1 mg/g for Hg²⁺, 132.4 mg/g for Pb²⁺, 83.5 mg/g for Cu²⁺, 54.1 mg/g for Cd²⁺, and 32.4 mg/g for Zn²⁺. The magnetic beads could be regenerated (up to ca. 97%) by a treatment with 0.1M HNO₃. These features make m‐poly(EGDMA–VTAZ) beads potential supports for heavy‐metal removal under a magnetic field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New metal chelate sorbent for albumin adsorption: Cibacron Blue F3GA-Zn(II) attached microporous poly(HEMA) membranes

Poly(2-hydroxyethyl methacrylate) [poly(HEMA)] membranes were prepared by UV-initiated photopolymerization of HEMA in the presence of an initiator (α-α′-azobis-isobutyronitrile, AIBN). The triazine dye Cibacron Blue F3GA was attached as an affinity ligand to poly(HEMA) membranes, covalently. These affinity membranes with a swelling ratio of 58% and containing 10.7 mmol Cibacron Blue F3GA/m² were used in the albumin adsorption studies. After dye-attachment, Zn(II) ions were chelated within the membranes via attached-dye molecules. Different amounts of Zn(II) ions [650–1440 mg Zn(II)/m²] were loaded on the membranes by changing the initial concentration of Zn(II) ions and pH. Bovine serum albumin (BSA) adsorption on these membranes from aqueous solutions containing different amounts of BSA at different pH was investigated in batch reactors. The nonspecific adsorption of BSA on the poly(HEMA) membranes was negligible. Cibacron Blue F3GA attachment significantly increased the BSA adsorption up to 92.1 mg BSA/m². Adsorption capacity was further increased when Zn(II) ions were attached (up to 144.8 mg BSA m²). More than 90% of the adsorbed BSA was desorbed in 1 h in the desorption medium containing 0.5M NaSCN at pH 8.0 and 0.025M EDTA at pH 4.9. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 657–664, 1998     

Preparation of a novel metal‐chelate affinity beads for albumin isolation from human plasma

In this study, we developed a novel approach to obtain a high protein‐adsorption capacity utilizing 2‐methacryloylamidohistidine (MAH) as a biollgand. MAH was synthesized by reacting methacryloyl chloride and histidine. Spherical beads, with an average size of 150–200 μm, were obtained by the radical suspension polymerization of MAH, ethyleneglycol dimethacrylate (EGDMA), and 2‐hydroxyethyl methacrylate (HEMA) conducted in an aqueous dispersion medium. p(EGDMA–HEMA–MAH) beads had a specific surface area of 17.6 m²/g. The synthesized MAH monomer was characterized by NMR. p(EGDMA–HEMA–MAH) beads were characterized by a swelling test, FTIR, and elemental analysis. Then, Cu(II) ions were incorporated into the beads and Cu(II) loading was found to be 0.96 mmol/g. These beads, with a swelling ratio of 65% and containing 1.6 mmol MAH/g, were used in the adsorption/desorption of human serum albumin (HSA) from both aqueous solutions and human serum. The adsorption of HSA onto p(EGDMA–HEMA–MAH) was low (8.8 mg/g). Cu(II) chelation onto the beads significantly increased the HSA adsorption (56.3 mg/g). The maximum HSA adsorption was observed at pH 8.0 Higher HSA adsorption was observed from human serum (94.6 mg HSA/g). Adsorptions of other serum proteins were obtained as 3.7 mg/g for fibrinogen and 8.5 mg/g for γ‐globulin. The total protein adsorption was determined as 107.1 mg/g. Desorption of HSA was obtained using a 0.1M Tris/HCI buffer containing 0.5M NaSCN. High desorption ratios (to 98% of the adsorbed HSA) were observed. It was possible to reuse Cu(II)‐chelated p(EGDMA–HEMA–MAH) beads without significant decreases in the adsorption capacities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2840–2847, 2003     

A novel highly copper(II)‐selective chelating ion exchanger based on poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) beads modified with aspartic acid derivative

Anchoring the hydroxyaspartic acid onto poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) (poly(GMA‐co‐EDMA)) beads or epoxysuccinic acid onto ammonium‐modified poly(GMA‐co‐EDMA) beads resulted in a novel chelating resin, which contained up to 0.37 mmol of the ligand per gram of resin. Batch extraction experiments showed a very high selectivity for Cu²⁺ over Zn²⁺ and Cd²⁺ ions in buffered solutions under competitive conditions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 913–916, 2001     

Vinyl triazole carrying metal‐chelated beads for the reversible immobilization of glucoamylase

Poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads with an average diameter of 100–200 μm were obtained by the copolymerization of ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer hydrogel bead composition was determined by elemental analysis and was found to contain 5 EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads were characterized by swelling studies and scanning electron microscopy (SEM). The specific surface area of the poly(EGDMA–VTAZ) beads was found 65.8 m²/g. Cu²⁺ ions were chelated on the poly(EGDMA–VTAZ) beads. The Cu²⁺ loading was 82.6 μmol/g of support. Cu²⁺‐chelated poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used in the immobilization of Aspergillus niger glucoamylase in a batch system. The maximum glucoamylase adsorption capacity of the poly(EGDMA–VTAZ)–Cu²⁺ beads was 104 mg/g at pH 6.5. The adsorption isotherm of the poly(EGDMA–VTAZ)–Cu²⁺ beads fitted well with the Langmuir model. Adsorption kinetics data were tested with pseudo‐first‐ and second‐order models. The kinetic studies showed that the adsorption followed a pseudo‐second‐order reaction model. The Michaelis constant value for the immobilized glucoamylase (1.15 mg/mL) was higher than that for free glucoamylase (1.00 mg/mL). The maximum initial rate of the reaction values were 42.9 U/mg for the free enzyme and 33.3 U/mg for the immobilized enzyme. The optimum temperature for the immobilized preparation of poly(EGDMA–VTAZ)–Cu²⁺–glucoamylase was 65°C; this was 5°C higher than that of the free enzyme at 60°C. The glucoamylase adsorption capacity and adsorbed enzyme activity slightly decreased after 10 batch successive reactions; this demonstrated the usefulness of the enzyme‐loaded beads in biocatalytic applications. The storage stability was found to increase with immobilization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive green HE‐4BD functionalized supermacroporous poly(hydroxyethyl methacrylate) cryogel for heavy metal removal

The aim of this study was to investigate the heavy metal adsorption performance of supermacroporous poly(hydroxyethyl methacrylate) [PHEMA] cryogel. The PHEMA cryogel was produced by cryo‐polymerization. The PHEMA cryogel was characterized by scanning electron microscopy (SEM). The PHEMA cryogel containing 385 μmol Reactive Green HE‐4BD/g were used in the adsorption studies. Adsorption capacity of the PHEMA cryogel for the metal ions, i.e., Cu²⁺, Cd²⁺, and Pb²⁺ were investigated in aqueous media containing different amounts of the ions (5–600 mg/L) and at different pH values (3.2–6.9). The maximum adsorption capacities of the PHEMA cryogel were 11.6 mg/g (56 μmol/g) for Pb²⁺, 24.5 mg/g (385 μmol/g) for Cu²⁺ and 29.1 mg/g (256 μmol/g) for Cd²⁺. The competitive adsorption capacities were 10.9 mg/g (52 μmol/g) for Pb²⁺, 22.1 mg/g for Cd²⁺ (196 μmol/g) and 23.2 mg/g (365 μmol/g) for Cu²⁺. The PHEMA/Reactive Green HE‐4BD cryogel exhibited the following metal ion affinity sequence on molar basis: Cu²⁺ > Cd²⁺ > Pb²⁺. The PHEMA/Reactive Green HE‐4BD cryogel can be easily regenerated by 50 mM EDTA with higher effectiveness. These features make the PHEMA/Reactive Green HE‐4BD cryogel a potential adsorbent for heavy metal removal. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Congo red- and Zn(II)-derivatized monosize poly(MMA-HEMA) microspheres as specific sorbent in metal chelate affinity of albumin

Monosize poly(methylmethacrylate-hydroxyethylmethacrylate) [poly(MMA-HEMA)] microspheres (4 μm in diameter) were produced by dispersion copolymerization of MMA and HEMA in an ethanol-water medium. Congo Red was attached to the poly(MMA-HEMA) microspheres, covalently. These Congo Red-derivatized microspheres were characterized by optical microscopy, Fourier transform infrared spectroscopy, and elemental analysis. Then, Zn(II) ions were incorporated by chelating with the immobilized Congo Red molecules. Different amounts of Zn(II) ions [1.2–17.6 mg of Zn(II)/g of polymer] were conjugated on the microspheres by changing the initial concentration of Zn(II) ions and pH. Bovine serum albumin (BSA) adsorption on these microspheres from aqueous solutions containing different amounts of BSA at different pH and ionic strengths was investigated in batch reactors. The nonspecific BSA adsorption on the plain poly(MMA-HEMA) microspheres was very low (0.7 mg of BSA/g of polymer). Congo Red derivatization significantly increased the BSA adsorption (up to 35.8 mg of BSA/g of polymer). A further increase in the adsorption capacity (up to 61.0 mg of BSA/g of polymer) was observed when Zn(II) ions were incorporated. More than 90% of the adsorbed BSA was desorbed in 1 h in the desorption medium containing 1.0M NaSCN at pH 8.0. © 1997 John Wiley & Sons, Inc.     

Formation of thermosensitive copolymer beads having phosphinic acid groups and adsorption ability for metal ions

Hydrophilic thermosensitive copolymer beads having phosphinic acid groups were prepared by suspension copolymerization of acryloyloxypropyl n‐octylphosphinic acid (APPO), N‐isopropyl acrylamide (NIPAAm), and tetraethyleneglycol dimethacrylate (4G). The thermosensitivity and the adsorption ability of the copolymer beads for metal ions beads were studied. The APPO‐NIPAAm‐4G copolymer beads were obtained in a good yield by suspension copolymerization of monomers (APPO, NIPAAm, and 4G) dissolved in chloroform, in a saturated Na₂SO₄ aqueous solution in the presence of surfactant and MgCO₃. The APPO‐NIPAAm‐4G copolymer beads had higher adsorption ability for lanthanide metal ions (Eu³⁺, Sm³⁺, Nd³⁺, or La³⁺) than for main transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺). Furthermore, it was also found that the APPO‐NIPAAm‐4G copolymer beads had selective adsorption ability between lanthanide metal ions, and the order of adsorption ability for lanthanide metal ions was as follows: Eu³⁺ > Sm³⁺ > Nd³⁺ > La³⁺. The selective adsorption for these metal ions from their mixed solutions was performed by both a batch method and a column method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 449–460, 2006     

Porous magnetic chelator support for albumin adsorption by immobilized metal affinity separation

Magnetic poly(2‐hydroxyethylmethacrylate) (mPHEMA) beads are modified by iminodiacetic acid (IDA) to implify the reactive groups and subsequent binding of Cu²⁺ ions to form metal chelate. mPHEMA beads, in the size range of 80–120 μm, were produced by a modified suspension polymerization technique. mPHEMA beads were characterized by swelling tests, electron spin resonance (ESR), FTIR, and scanning electron microscopy (SEM). Important results obtained in this study are as follows. The swelling ratio of mPHEMA beads was 34%. The presence of magnetite particles in the polymeric structure was confirmed by ESR. FTIR data confirmed that the magnetic polymer beads were modified with functional groups IDA. The mPHEMA beads have a spherical shape and porous structure. The effect of pH and concentration of human serum albumin (HSA), on the adsorption of HSA to the metal‐chelated magnetic beads, were examined in a batch reactor. Most importantly, the magnetic beads had little nonspecific adsorption for HSA (0.5 mg/g) before introducing IDA groups. Cu²⁺ chelation increased the HSA adsorption up to 28.4 mg/g. Adsorption behavior can be described at least approximately with the Langmuir equation. Regeneration of the metal‐chelated magnetic beads was easily performed with 1.0M NaSCN, pH 8.0, followed by washing with distilled water and reloading with Cu²⁺. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2501–2510, 2004