Porous dye affinity beads for nickel adsorption from aqueous solutions: A kinetic study

We investigated a new adsorbent system, Reactive Red 120 attached poly(2‐hydroxyethyl methacrylate ethylene dimethacrylate) [poly(HEMA–EDMA)] beads, for the removal of Ni²⁺ ions from aqueous solutions. Poly(HEMA–EDMA) beads were prepared by the modified suspension copolymerization of 2‐hydroxyethyl methacrylate and ethylene dimethacrylate. Reactive Red 120 molecules were covalently attached to the beads. The beads (150–250 μm), having a swelling ratio of 55% and carrying 25.5 μmol of Reactive Red 120/g of polymer, were used in the removal of Ni²⁺ ions. The adsorption rate and capacity of the Reactive Red 120 attached poly(HEMA–EDMA) beads for Ni²⁺ ions was investigated in aqueous media containing different amounts of Ni²⁺ ions (5–35 mg/L) and having different pH values (2.0–7.0). Very high adsorption rates were observed at the beginning, and adsorption equilibria were then gradually achieved in about 60 min. The maximum adsorption of Ni²⁺ ions onto the Reactive Red 120 attached poly(HEMA–EDMA) beads was 2.83 mg/g at pH 6.0. The nonspecific adsorption of Ni²⁺ ions onto poly(HEMA–EDMA) beads was negligible (0.1 mg/g). The desorption of Ni²⁺ ions was studied with 0.1M HNO₃. High desorption ratios (>90%) were achieved. The intraparticle diffusion rate constants at various temperatures were calculated as k_20°C = 0.565 mg/g min^0.5, k_30°C = 0.560 mg/g min^0.5, and k_40°C = 0.385 mg/g min^0.5. Adsorption–desorption cycles showed the feasibility of repeated use of this novel adsorbent system. The equilibrium data fitted very well both Langmuir and Freundlich adsorption models. The pseudo‐first‐order kinetic model was used to describe the kinetic data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:5056–5065, 2006     

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     

Specific sorbents for bilirubin removal from human plasma: Congo red-modified poly(EGDMA/HEMA) microbeads

Congo Red-modified poly(EGDMA–HEMA) microbeads were investigated as a specific sorbent for bilirubin removal from human plasma. Poly(EGDMA–HEMA) microbeads were prepared by a modified suspension copolymerization technique. Congo Red was covalently incorporated into the poly(EGDMA–HEMA) microbeads via condensation reactions between the aromatic amine groups of the dyes and the hydroxyl groups of the HEMA, under alkaline conditions. Bilirubin adsorption was investigated from hyperbilirubinemic human plasma on the poly(EGDMA–HEMA) microbeads containing different amounts of attached Congo Red (between 2.5 and 14.6 μmol/g). The nonspecific bilirubin adsorption on the unmodified poly(EGDMA–HEMA) microbeads were 0.32 mg/g from human plasma. High adsorption rates were observed at the beginning, and the adsorption equilibrium was then gradually achieved in about 30–60 min. Much higher bilirubin adsorption values, up to 11.7 mg/g, were obtained with the Congo Red-modified microbeads especially at 37°C. The numbers (as μmol) of bilirubin molecules to albumin molecules adsorbed on the sorbent microbeads were in the range of 15–20, which showed that bilirubin molecules were preferentially adsorbed to the Congo Red-modified microbeads. Bilirubin adsorption increased with increasing temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:373–380, 1998     

Synthesis and characterization of poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) copolymer beads for heavy‐metal removal

We prepared poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads (average diameter = 150–200 μm) by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer composition was characterized by elemental analysis and found to contain five EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads had a specific surface area of 65.8 m²/g. Poly(EGDMA–VTAZ) beads were characterized by Fourier transform infrared spectroscopy, elemental analysis, surface area measurements, swelling studies, and scanning electron microscopy. Poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used for the heavy‐metal removal studies. The adsorption capacities of the beads for Cd(II), Hg(II), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(EGDMA–VTAZ) beads were 85.7 mg/g (0.76 mmol/g) for Cd(II), 134.9 mg/g (0.65 mmol/g) for Pb(II), and 186.5 mg/g (0.93 mmol/g) for Hg(II). The affinity order toward triazole groups on a molar basis was observed as follows: Hg(II) > Cd(II) > Pb(II). pH significantly affected the adsorption capacity of the VTAZ‐incorporated beads. The equilibrium data were well fitted to the Redlich–Peterson isotherm. Consideration of the kinetic data suggested that chemisorption processes could have been the rate‐limiting step in the adsorption process. Regeneration of the chelating‐beads was easily performed with 0.1M HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4276–4283, 2006     

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.     

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     

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     

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.     

Poly(acrylamide‐allyl glycidyl ether) cryogel as a novel stationary phase in dye‐affinity chromatography

Poly(acrylamide‐allyl glycidyl ether) [poly(AAm‐AGE)] cryogel was prepared by bulk polymerization which proceeds in an aqueous solution of monomers frozen inside a glass column (cryo‐polymerization). After thawing, the monolithic cryogel contains a continuous polymeric matrix having interconnected pores of 10–100 μm size. Cibacron Blue F3GA was immobilized by covalent binding onto poly(AAm‐AGE) cryogel via epoxy groups. Poly(AAm‐AGE) cryogel was characterized by swelling studies, FTIR, scanning electron microscopy, and elemental analysis. The equilibrium swelling degree of the poly(AAm‐AGE) monolithic cryogel was 6.84 g H₂O/g cryogel. Poly(AAm‐AGE) cryogel containing 68.9 μmol Cibacron Blue F3GA/g was 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 amount of HSA adsorption from aqueous solution in acetate buffer was 27 mg/g at pH 5.0. Higher HSA adsorption value was obtained from human plasma (up to 74.2 mg/g). Desorption of HSA with a purity of 92% from Cibacron Blue F3GA attached poly(AAm‐AGE) cryogel was achieved using 0.1M Tris/HCl buffer containing 0.5M NaCl. It was observed that HSA could be repeatedly adsorbed and desorbed with poly(AAm‐AGE) cryogel without significant loss in the adsorption capacity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Adsorption of IgG on spacer‐arm and L‐arginine ligand attached poly(GMA/MMA/EGDMA) beads

This work presents data on human immunoglobulin G (HIgG) adsorption onto L ‐arginine ligand attached poly(GMA/MMA/EGDMA)‐based affinity beads which were synthesized from methyl methacrylate (MMA) and glycidiyl methacrylate (GMA) in the presence of a crosslinker (i.e., ethylene glycol dimethacrylate; EGDMA) by suspension polymerization. The epoxy groups of the poly(GMA/MMA/EGDMA) beads were converted into amino groups after reaction with ammonia or 1,6‐diaminohexane (i.e., spacer‐arm). With L ‐arginine as a ligand, it was covalently immobilized on the aminated (poly(GMA/MMA/EGDMA)‐ AA) and/or the spacer‐arm attached (poly(GMA/MMA/EGDMA)‐SA) beads, using glutaric dialdehyde as a coupling agent. Both affinity poly(GMA/MMA/EGDMA)‐based beads were used in HIgG adsorption/desorption studies under defined pH, ionic strength, or temperature conditions in a batch reactor, using acid‐treated poly(GMA/MMA/EGDMA) beads as a control system. The poly(GMA/MMA/EGDMA)‐SA affinity beads resulted in an increase in the adsorption capacity to HIgG compared with the aminated counterpart (i.e., poly(GMA/MMA/EGDMA)‐AA). The maximum adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA affinity beads were found to be 112.36 and 142 mg g^?1, and the affinity constants (K_d), evaluated by the Langmuir model, were 2.48 × 10^?7 and 6.98 × 10^?7M, respectively. Adsorption capacities of the poly(GMA/MMA/EGDMA)‐AA and poly(GMA/MMA/EGDMA)‐SA were decreased with HIgG by increasing the ionic strength adjusted with NaCl. Adsorption kinetic of HIgG onto both affinity adsorbents was analyzed with first‐ and second‐order kinetic equations. The first‐order equation fitted well with the experimental data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 672–679, 2007     

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads

Metal chelating properties of Cibacron Blue F3GA‐derived poly(EGDMA‐HEMA) microbeads have been studied. Poly(EGDMA‐HEMA) microbeads were prepared by suspension copolymerization of ethylene glycol dimethacrylate (EGDMA) and hydroxy‐ethyl methacrylate (HEMA) by using poly(vinyl alcohol), benzoyl peroxide, and toluene as the stabilizer, the initiator, and the pore‐former, respectively. Cibacron Blue F3GA was covalently attached to the microbeads via the nucleophilic substitution reaction between the chloride of its triazine ring and the hydroxyl groups of the HEMA, under alkaline conditions. Microbeads (150–200 μm in diameter) with a swelling ratio of 55%, and carrying 16.5 μmol Cibacron Blue F3GA/g polymer were used in the adsorption/desorption studies. Adsorption capacity of the microbeads for the selected metal ions, i.e., Cu(II), Zn(II), Cd(II), Fe(III), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–200 ppm) and at different pH values (2.0–7.0). The maximum adsorptions of metal ions onto the Cibacron Blue F3GA‐derived microbeads were 0.19 mmol/g for Cu(II), 0.34 mmol/g for Zn(II), 0.40 mmol/g for Cd(II), 0.91 mmol/g for Fe(III), and 1.05 mmol/g for Pb(II). Desorption of metal ions were studied by using 0.1 M HNO₃. High desorption ratios (up to 97%) were observed in all cases. Repeated adsorption/desorption operations showed the feasibility of repeated use of this novel sorbent system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1397–1403, 1999     

Poly(vinylbenzylchloride) beads grafted with polymer brushes carrying hydrazine ligand for reversible enzyme immobilization

Poly(glycidylmethacrylate), p(GMA), brush grafted poly(vinylbenzyl chloride/ethyleneglycol dimethacrylate), p(VBC/EGDMA), beads were prepared by suspension polymerization and the beads were grafted with poly(glycidyl methacrylate), p(GMA), via surface‐initiated atom transfer radical polymerization aiming to construct a material surface with fibrous polymer. The epoxy groups of the fibrous polymer were reacted with hydrazine (HDZ) to create affinity binding site on the support for adsorption of protein. The influence of pH, and initial invertase concentration on the immobilization capacity of the p(VBC/EGDMA‐g‐GMA)‐HDZ beads has been investigated. Maximum invertase immobilization onto hydrazine functionalized beads was found to be 86.7 mg/g at pH 4.0. The experimental equilibrium data obtained invertase adsorption onto p(VBC/EGDMA‐g‐GMA)‐HDZ affinity beads fitted well to the Langmuir isotherm model. It was shown that the relative activity of immobilized invertase was higher than that of the free enzyme over broader pH and temperature ranges. The K_m and V_max values of the immobilized invertase were larger than those of the free enzyme. After inactivation of enzyme, p(VBC/EGDMA‐g‐GMA)‐HDZ beads can be easily regenerated and reloaded with the enzyme for repeated use. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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     

Human serum albumin adsorption on poly[(glycidyl methacrylate)‐co‐(methyl methacrylate)] beads modified with a spacer‐arm‐attached L‐histidine ligand

Poly(GMA/MMA) beads were synthesized from glycidyl methacrylate (GMA) and methyl methacrylate (MMA) in the presence of a cross‐linker (i.e. ethyleneglycol dimethacrylate) (EGDMA) via suspension polymerization. The epoxy groups of the poly(GMA/MMA) beads were converted into amino groups with either ammonia or 1,6‐diaminohexane (i.e. spacer‐arm). An L ‐histidine ligand was then covalently immobilized on the aminated (poly(GMA/MMA)‐AH) and/or the spacer‐arm attached (poly(GMA/MMA)‐SAH) beads using glutaric dialdehyde as a coupling agent. Both affinity adsorbents were used in human serum albumin (HSA) adsorption/desorption studies under defined pH, ionic strength or temperature conditions in a batch reactor. The spacer‐arm attached affinity adsorbent resulted in an increase in the adsorption capacity to HSA when compared to the aminated counterpart (i.e. poly(GMA/MMA)‐AH). The maximum adsorption capacities of the affinity adsorbents were found to be significantly high, i.e. 43.7 and 80.2 mg g^?1 (of the beads), while the affinity constants, evaluated by the Langmuir model, were 3.96 × 10^?7 and 9.53 × 10^?7 mol L^?1 for poly(GMA/MMA)‐AH and poly(GMA/MMA)‐SAH, respectively. The adsorption capacities of the affinity adsorbents were decreased for HSA by increasing the ionic strength, adjusted with NaCl. The adsorption kinetics of HSA were analysed by using pseudo‐first and pseudo‐second‐order equations. The second‐order equation fitted well with the experimental data. Copyright © 2005 Society of Chemical Industry     

Nonporous monosize polymeric sorbents: Dye and metal chelate affinity separation of lysozyme

Lysozyme adsorption onto dye‐attached nonporous monosize poly(2‐hydroxyethyl‐methacrylate‐methylmethacrylate) [poly(HEMA‐MMA)] microspheres was investigated. Poly(HEMA‐MMA) microspheres were prepared by dispersion polymerization. The monochloro‐triazine dye, Cibacron Blue F3GA, was immobilized covalently as dye–ligand. These dye‐affinity microspheres were used in the lysozyme adsorption–desorption studies. The effect of initial concentration of lysozyme and medium pH on the adsorption efficiency of dye‐attached and metal‐chelated microspheres were studied in a batch reactor. Effect of Cu(II) chelation on lysozyme adsorption was also studied. The nonspecific adsorption of lysozyme on the poly(HEMA‐MMA) microspheres was 3.6 mg/g. Cibacron Blue F3GA attachment significantly increased the lysozyme adsorption up to 247.8 mg/g. Lysozyme adsorption capacity of the Cu(II) incorporated microspheres (318.9 mg/g) was greater than that of the Cibacron Blue F3GA‐attached microspheres. Significant amount of the adsorbed lysozyme (up to 97%) was desorbed in 1 h in the desorption medium containing 1.0M NaSCN at pH 8.0 and 25 mM EDTA at pH 4.9. In order to examine the effects of separation conditions on possible conformational changes of lysozyme structure, fluorescence spectrophotometry was employed. We conclude that dye‐ and metal‐chelate affinity chromatography with poly(HEMA‐MMA) microspheres can be applied for lysozyme separation without causing any significant changes and denaturation. Repeated adsorption/desorption processes showed that these novel dye‐attached monosize microspheres are suitable for lysozyme adsorption. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 115–124, 2000     

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.     

Cibacron Blue F3GA‐attached magnetic poly(2‐hydroxyethyl methacrylate) beads for human serum albumin adsorption

An affinity dye ligand, Cibacron Blue F3GA, was covalently attached onto magnetic poly(2‐hydroxyethyl methacrylate) (mPHEMA) beads for human serum albumin (HSA) adsorption from both aqueous solutions and human plasma. The mPHEMA beads, in the size range of 80 to 120 µm, were prepared by a modified suspension technique. Cibacron Blue F3GA molecules were incorporated on to the mPHEMA beads. The maximum amount of Cibacron Blue F3GA attachment was obtained as 68.3 µmol g^?1. HSA adsorption onto unmodified and Cibacron Blue F3GA‐attached mPHEMA beads was investigated batchwise. The non‐specific adsorption of HSA was very low (1.8 mg g^?1). Cibacron Blue F3GA attachment onto the beads significantly increased the HSA adsorption (94.5 mg g^?1). The maximum HSA adsorption was observed at pH 5.0. Higher HSA adsorption was observed from human plasma (138.3 mg HSA g^?1). Desorption of HSA from Cibacron Blue F3GA‐attached mPHEMA beads was obtained by using 0.1 M Tris/HCl buffer containing 0.5 M NaSCN. High desorption ratios (up to 98% of the adsorbed HSA) were observed. It was possible to re‐use Cibacron Blue F3GA‐attached mPHEMA beads without any significant decreases in their adsorption capacities. Copyright © 2004 Society of Chemical Industry     

Adsorption of Cr(VI) ions onto poly(ethylene glycol dimethacrylate‐1‐vinyl‐1,2,4‐triazole)

Poly(ethylene glycol dimethacrylate‐1‐vinyl‐1,2,4‐triazole) [poly(EGDMA‐VTAZ)] beads (average diameter = 150–200 μm) were prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). Poly(EGDMA‐VTAZ) beads were characterized by swelling studies and scanning electron microscope (SEM). The adsorption of Cr(VI) from solutions was carried at different contact times, Cr(VI) concentrations, pH, and temperatures. High adsorption rates were achieved in about 240 min. The amount of Cr(VI) adsorbed increased with increasing concentration and decreasing pH and temperature. The intraparticle diffusion rate constants at various temperatures were calculated. Adsorption isotherms of Cr(VI) onto poly(EGDMA‐VTAZ) have been determined and correlated with common isotherm equations such as Langmuir and Freundlich isotherm models. The Langmuir isotherm model appeared to fit the isotherm data better than the Freundlich isotherm model. The pseudo first‐order kinetic model was used to describe the kinetic data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy changes. The dimensionless separation factor (R_L) showed that the adsorption of metal ions onto poly(EGDMA‐VTAZ) was favorable. It was seen that values of distribution coefficient (K_D) decreasing with Cr(VI) concentration in solution at equilibrium (C_e) indicated that the occupation of activate surface sites of adsorbent increased with Cr(VI). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009