Cover Image,Volume 62, Issue 8

A novel three-component covalent organic polymer (COP) named SLEL-6 was prepared based on Schiff base chemistry through a multi-component method for ciprofloxacin removal from an aqueous solution. It could be embedded in sodium alginate (SA) to obtain spherical COP/SA composite beads (SLEL-6/SA beads) with enhanced adsorption ability and boosted recyclability. Details are found in the article from Yangxue Li and colleagues. DOI: 10.1002/pol.20230258

     

Comparative Adsorption of Lead(II) on Flake and Bead‐Types of Chitosan

The adsorption of Pb(II) ions from aqueous solutions by chitosan flakes and beads was studied. The chitosan beads were prepared by casting an acidic chitosan solution into alkaline solution. Experiments were carried out as a function of pH, agitation period and initial concentration of Pb²⁺ ions. The uptake of Pb²⁺ ions from aqueous solution was determined from changes in concentration as measured by atomic absorption spectroscopy. The maximum uptake of Pb²⁺ ions on chitosan beads was greater than that on chitosan flakes. Adsorption isothermal data could be interpreted by the Langmuir equation. The experimental data of the adsorption equilibrium from Pb²⁺ ion solutions correlated well with the Langmuir isotherm equation. SEM analyses were also conducted for visual examination of the chitosan flakes and beads. Physical properties including surface area and average pore diameter were characterized by N₂ adsorption experiment.     

Adsorption of chromium from aqueous solution using chitosan beads

A basic investigation on the removal of Cr(III) and Cr(VI) ions from aqueous solution by chitosan beads was conducted in a batch adsorption system. The chitosan beads were prepared by casting an acidic chitosan solution into an alkaline solution. The influence of different experimental parameters; pH, agitation period and different concentration of Cr(III) and Cr(VI) ions was evaluated. A pH 5.0 was found to be an optimum pH for Cr(III) adsorption, and meanwhile pH 3.0 was the optimum pH for the adsorption of Cr(VI) onto chitosan beads. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherms and isotherm constants for the adsorption of Cr(III) and Cr(VI) onto chitosan beads. Results indicated that Cr(III) and Cr(VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacities of Cr(III) and Cr(VI) ions onto chitosan beads were 30.03 and 76.92 mg g⁻¹, respectively. Results showed that chitosan beads are favourable adsorbents. The Cr(III) and Cr(VI) ions can be removed from the chitosan beads by treatment with an aqueous EDTA solution.     

Using Zeolite/Polyvinyl alcohol/sodium alginate nanocomposite beads for removal of some heavy metals from wastewater

Functionalized Polyvinyl alcohol/sodium alginate (PVA/SA) beads were synthesized via blending Polyvinyl alcohol (PVA) with sodium alginate (SA) and the glutaraldehyde was used as a cross-linking agent. The zeolite nanoparticles (Zeo NPs) incorporated PVA/SA resulting Zeo/PVA/SA nanocomposite (NC) beads were synthesized for removal of some heavy metal from wastewater. The synthesizes beads were characterized via Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction (XRD), particle size analyzer (PSA), and scanning electron microscope (SEM). The adsorption kinetics of the selected metal ions onto Zeo/PVA/SA NC beads followed the pseudo-first-order model (PFO) and the adsorption isotherm model was well fitted by the Langmuir model. Moreover, the thermodynamic studies were also examined; the outcomes showed that the adsorption mechanisms of the selective metal ions were endothermic, the chemical in nature, spontaneous adsorption on the surface of the Zeo/PVA/SA NC beads. The removal efficiency using Zeo/PVA/SA NC modified beads reached maximum at the pH value of 6.0 for Pb²⁺, Cd²⁺, Sr²⁺, Cu²⁺, Zn²⁺, Ni²⁺, Mn²⁺ and Li²⁺ with 99.5, 99.2, 98.8, 97.2, 95.6, 93.1, 92.4 and 74.5%, respectively, while the highest removal are achieved at pH = 5 for Fe³⁺ and Al³⁺ with 96.5 and 94.9%, respectively and decreased at lower or higher pH values. The survival count (%) of the E. coli cells were 34% on the SA beads, 11% on the PVA/SA, and 1% on the Zeo/PVA/SA NC modified beads, after 120 min exposure at 25 °C. Reusability experimental displays that the synthesized beads preserved a significant decrease in the sorption capacity after 10 repeating cycles. The Zeo/PVA/SA NC beads were able to eliminate 60–99.8% of Al³⁺, Fe³⁺, Cr³⁺, Co²⁺, Cd²⁺, Zn²⁺, Mn²⁺, Ni²⁺, Cu²⁺, Li²⁺, Sr²⁺, Si²⁺, V²⁺, and Pb²⁺ ions from the natural wastewater samples collected from 10th Ramadan City, Cairo, Egypt.     

Husk of Agarwood Fruit-Based Hydrogel Beads for Adsorption of Cationic and Anionic Dyes in Aqueous Solutions

Hydrogel beads based on the husk of agarwood fruit (HAF)/sodium alginate (SA), and based on the HAF/chitosan (CS) were developed for the removal of the dyes, crystal violet (CV) and reactive blue 4 (RB4), in aqueous solutions, respectively. The effects of the initial pH (2–10) of the dye solution, the adsorbent dosage (0.5–3.5 g/L), and contact time (0–540 min) were investigated in a batch system. The dynamic adsorption behavior of CV and RB4 can be represented well by the pseudo-second-order model and pseudo-first-order model, respectively. In addition, the adsorption isotherm data can be explained by the Langmuir isotherm model. Both hydrogel beads have acceptable adsorption selectivity and reusability for the study of selective adsorption and regeneration. Based on the effectiveness, selectivity, and reusability of these hydrogel beads, they can be treated as potential adsorbents for the removal of dyes in aqueous solutions.     

Dextran-grafted cation exchanger based on superporous agarose gel: Adsorption isotherms,uptake kinetics and dynamic protein adsorption performance

A novel chromatographic medium for high-capacity protein adsorption was fabricated by grafting dextran (40 kDa) onto the pore surfaces of superporous agarose (SA) beads. The bead was denoted as D-SA. D-SA, SA and homogeneous agarose (HA) beads were modified with sulfopropyl (SP) group to prepare cation exchangers, and the adsorption and uptake of lysozyme on all three cation-exchange chromatographic beads (SP-HA, SP-SA and SP-D-SA) were investigated at salt concentrations of 6–50 mmol/L. Static adsorption experiments showed that the adsorption capacity of SP-D-SA (2.24 mmol/g) was 78% higher than that of SP-SA (1.26 mmol/g) and 54% higher than that of SP-HA (1.45 mmol/g) at a salt concentration of 6 mmol/L. Moreover, salt concentration had less influence on the adsorption capacity and dissociation constant of SP-D-SA than it did on SP-HA, suggesting that dextran-grafted superporous bead is a more potent architecture for chromatographic beads. In the dynamic uptake of lysozyme to the three cation-exchange beads, the D_e/D₀ (the ratio of effective pore diffusivity to free solution diffusivity) values of 1.6–2.0 were obtained in SA-D-SA, indicating that effective pore diffusivities of SP-D-SA were about two times higher than free solution diffusivity for lysozyme. At 6 mmol/L NaCl, the D_e value in SA-D-SA (22.0 × 10⁻¹¹ m²/s) was 14.4-fold greater than that in SP-HA. Due to the superior uptake kinetics in SA-D-SA, the highest dynamic binding capacity (DBC) and adsorption efficiency (the ratio of DBC to static adsorption capacity) was likewise found in SP-D-SA. It is thus confirmed that SP-D-SA has combined the advantages of superporous matrix structure and drafted ligand chemistry in mass transport and offers a new opportunity for the development of high-performance protein chromatography.     

Synthesis and applications of Ce(III)-imprinted polymer based on attapulgite as the sacrificial support material for selective separation of cerium(III) ions

A surface-imprinting technique combined with a sacrificial support process was established to synthesize a novel Ce(III)-imprinted polymer (CIP) in which attapulgite acts as the sacrificial support material. The CIP was compared with attapulgite, non-imprinted polymer (NIP), and with a Ce(III)-imprinted polymer where attapulgite acts as the support material (AIP). Fourier transmission infrared spectrometry, scanning electron microscopy, transmission electron microscopy, simultaneous thermogravimetry, nitrogen sorption, and laser particle sizing were employed, and an imprinting mechanism is suggested. Batch experiments were performed to evaluate adsorption kinetics, selective recognition, adsorption isotherms, desorption and regeneration performances of the CIP. The CIP offers fast adsorption kinetics for Ce³⁺, and the maximum adsorption capacity is 130 mg?g^?1, which is larger than that of AIP and attapulgite. The absorption abilities of Ce³⁺ from aqueous solutions followed the order CIP>AIP>attapulgite>NIP. CIP could be reused four times with only about 16% and 18% loss of adsorption capacity in pure Ce³⁺ solution and potentially interfering ion solution, respectively. The method was applied to the separation and determination of trace Ce³⁺ in river sediments. The relative standard deviation of the method is 2.6% (n?=?6.0), and the detection limit (3σ) is 57 ng?L^?1.     

Thermokinetics simulation for multi-walled carbon nanotubes with sodium alginate by advanced kinetics and technology solutions

To accomplish an effective analysis of adsorption, the strong acid dye from aqueous solution of sodium alginate (SA) and multi-walled carbon nanotubes (MWCNTs) composite gel beads were used as important parameters. Differential scanning calorimetry (DSC) was used to measure the heat of breakdown reaction. The experimental conditions were set at 0.5, 1, 2, 4, and 8 °C min^?1, and the temperature range was 30–300 °C. The heating rates and the temperature range were set as follows: Four kinds of proportion in this experiment contained 2 SA % w/v (SA), 0.03, 0.09, 0.18, 0.36 % w/v (MWCNTs), and 10 % w/v calcium chloride, respectively. Four samples, 5, 6, 7, 8, and 9 mg, were used to detect the experimental data. It contributed to understanding the reaction for the distinctive MWCNTs. With the thermokinetic data by isoconversional approach obtained from advanced kinetics and technology solutions (AKTS), the related thermal safety information can be obtained from the thermal reaction of MWCNTs. Valuable parameters, such as activation energy (E _a) and heat of decomposition, can be applied in operation, including adsorption and desorption processes. After DSC tests, and under the four compositions of SA/MWCNTs, at different heating rates of 0.5, 1, 2, 4, and 8 °C min^?1, primarily we found that when the heating rate was increased, exothermic onset temperature would increase gradually. After analyzing E _a value by isoconversional kinetics, we learned that in four different adsorption compositions, SA/MWCNTs_0.03 (161.20 kJ mol^?1) was the minimum. Among them, the highest value was SA/MWCNTs_0.18 (220.48 kJ mol^?1). However, in this study, for SA/MWCNTs compositions we found that E _a value will drop in the final material SA/MWCNTs_0.36. Accordingly, if the ratio of SA and calcium chloride was fixed, then different compositions of the MWCNTs would affect adsorption efficiency of SA/MWCNTs and E _a variation.     

Adsorption of Hg(II) Ions onto Binary Biopolymeric Beads of Carboxymethyl Cellulose and Alginate

The removal of Hg(II) ions from aqueous solution by adsorption onto cross-linked polymeric beads of carboxymethyl cellulose (CMC) and sodium alginate was studied at fixed pH (6) and room temperature 28 ± 0.2°C. The cross-linked polymeric beads were characterized by FTIR spectra. Sorption capacity of the polymer for the mercury ions was investigated in aqueous media consisting different amounts of mercury ions (2.5 to 100 mg dm^?3) and at different pH values (2 to 8). Adsorption behavior of Hg(II) ions could be modeled using both the Langmuir and Freundlich isotherms. The dynamic nature of adsorption was quantified in terms of several kinetic constants such as rate constants for adsorption (k₁) and Lagergreen rate constant (K_ad). The influence of various experimental parameters such as effect of pH, contact time, solid-to-liquid ratio, salt effect, and temperature effect etc. were investigated on the adsorption of Hg(II) ions.     

Assesment of dimethyl phthalate removal from aqueous phase using barium hexaferrite containing magnetic beads

The barium hexaferrite (BaFe(12)O(19)) containing magnetic poly (ethylene glycol dimethacrylate-vinyl pyridine; mag-poly [EGDMA-VP]) beads (average diameter=53-212 μm) were synthesized and characterized. Their use as an adsorbent in the removal of dimethyl phthalate (DMP) from an aqueous solution was investigated. The mag-poly (EGDMA-VP) beads were prepared by copolymerizing of 4-vinyl pyridine (VP) with ethylene glycol dimethacrylate (EGDMA). The mag-poly (EGDMA-VP) beads were characterized by N(2) adsorption/desorption isotherms (BET), vibrating sample magnetometer (VSM), X-ray powder diffraction (XRD), elemental analysis, scanning electron microscope (SEM), and swelling studies. At a fixed solid/solution ratio, the various factors affecting the adsorption of DMP from aqueous solutions such as pH, initial concentration, contact time, and temperature were analyzed. The maximum DMP adsorption capacity of the mag-poly (EGDMA-VP) beads was determined as 96.2 mg/g at pH 3.0, 25 °C. All the isotherm data can be fitted with both the Langmuir and the Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The thermodynamic parameters obtained indicated the exothermic nature of the adsorption. The DMP adsorption capacity did not change after 10 batch successive reactions, demonstrating the usefulness of the magnetic beads in applications.     

Preparation of ion-exchange beads based on poly(methacrylic acid) brush grafted chitosan beads: Isolation of lysozyme from egg white in batch system

Poly(methacrylic acid) brush grafted crosslinked-chitosan (chitosan-g-poly(MAA)) beads were prepared in two sequential steps: in the first step, chitosan beads were prepared by phase-inversion technique and then were crosslinked with epichlorohydrin under alkaline condition; in the second step, the graft copolymerization of methacrylic acid onto the chitosan beads was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan-g-poly(MAA) beads were first used as an ion exchange support for adsorption of lysozyme (LYZ) from aqueous solution. The influence of pH, equilibrium time, ionic strength and initial LYZ concentration on the adsorption capacity of the chitosan-g-poly(MAA) ion-exchange beads has been investigated in a batch system. Maximum LYZ adsorption onto chitosan-g-poly(MAA) beads was found to be 65.7 mg/g at pH 6.0. The experimental equilibrium data obtained LYZ adsorption onto chitosan-g-poly(MAA) ion-exchange beads fitted well to the Langmuir isotherm model. Kinetics parameters of this adsorption system were also analyzed by using the equilibrium experimental data. The result of kinetic analyzed for LYZ adsorption onto ion-exchange beads showed that the second order rate equation was favourable. Finally, the chitosan-g-poly(MAA) ion-exchange beads were used for the purification of LYZ from egg white in batch system and the purity of the eluted LYZ from ion-exchange chitosan-g-poly(MAA) beads was determined as 94% by HPLC from single step purification.     

Simultaneous adsorption of tetracycline,amoxicillin, and ciprofloxacin by pistachio shell powder coated with zinc oxide nanoparticles

A new adsorbent formed from pistachio shell powder that was coated with ZnO nanoparticles (CPS) was examined in terms of simultaneous adsorption of tetracycline (TEC), amoxicillin (AMO), and ciprofloxacin (CIP) from an aqueous solution. Initially, the characterization properties of a CPS-like surface morphology, functional groups, and structure were obtained using advanced analysis of TEM, SEM, XRD, EDS, and FT-IR. Post coating with ZnO nanoparticles, several surface and structural characteristics relating to the adsorption ability of the pistachio shell were significantly improved. The correlation of the kinetic data by a pseudo second-order model was successful for three antibiotics. High compatibility resulted between the TEC and CIP isotherm data and the Fruendlich model. However, the Langmuir model produced a better fit to the AMO isotherm curves. In addition, its spontaneous and exothermic nature was the main feature for the adsorption process of the three antibiotics onto CPS. Through the results, the chemical adsorption has been governed by the AMO, CIP, and TEC reaction onto the homogeneous and heterogeneous sites of CPS surfaces. The CPS exhibited a highest adsorption capacity for AMO (132.240 mg/g), then for TEC (98.717 mg/g), and CIP (92.450 mg/g). These results place CPS one among the highly efficient adsorbents that can be used to eradicate wastewater containing antibiotics.     

Highly Porous Hydroxyapatite/Graphene Oxide/Chitosan Beads as an Efficient Adsorbent for Dyes and Heavy Metal Ions Removal

Dye and heavy metal contaminants are mainly aquatic pollutants. Although many materials and methods have been developed to remove these pollutants from water, effective and cheap materials and methods are still challenging. In this study, highly porous hydroxyapatite/graphene oxide/chitosan beads (HGC) were prepared by a facile one-step method and investigated as efficient adsorbents. The prepared beads showed a high porosity and low bulk density. SEM images indicated that the hydroxyapatite (HA) nanoparticles and graphene oxide (GO) nanosheets were well dispersed on the CTS matrix. FT-IR spectra confirmed good incorporation of the three components. The adsorption behavior of the obtained beads to methylene blue (MB) and copper ions was investigated, including the effect of the contact time, pH medium, dye/metal ion initial concentration, and recycle ability. The HGC beads showed rapid adsorption, high capacity, and easy separation and reused due to the porous characteristics of GO sheets and HA nanoparticles as well as the rich negative charges of the chitosan (CTS) matrix. The maximum sorption capacities of the HGC beads were 99.00 and 256.41 mg g⁻¹ for MB and copper ions removal, respectively.     

碳纳米管复合微球修饰L-色氨酸及其对LDL的吸附性能

本文以多孔碳纳米管/活性炭复合微球为载体, 以L-色氨酸为配基, 采用环氧氯丙烷偶联法, 制得修饰L-色氨酸的碳纳米管/活性炭复合微球(L-CNTs/AC)。采用扫描电镜、氮气吸附、傅立叶红外光谱、热分析、X射线光电子能谱等对复合微球进行表征;通过体外静态吸附法对其低密度脂蛋白(LDL)吸附能力进行初步研究。结果表明:环氧氯丙烷偶联法可接枝上L-色氨酸。复合微球中碳纳米管加入量越多, 对LDL的吸附能力越强;当碳纳米管加入量为45wt%时, 对LDL的吸附量达4.623 mg·g^-1, 是未添加碳纳米管的2.3倍多。这是因为碳纳米管不仅可促进复合微球中20~100 nm孔的形成, 而且还可促进复合微球配基修饰量的增多, 从而大大增强了复合微球对LDL的吸附能力。此复合微球可望开发成一种新型的血液灌流LDL吸附剂。     

A Novel Affinity Support Material for the Separation of Immunoglobulin G from Human Plasma

2‐Methacrylamidohistidine (MAH) as a pseudospecific ligand was synthesized from methacryl chloride and histidine. Spherical beads with an average size of 50–63 μm were obtained by the radical suspension polymerization of MAH and 2‐hydroxyethyl methacrylate (HEMA) conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, P(HEMA‐co‐MAH) beads had a specific surface area of 17.6 m²·g^–1. Synthesized MAH was characterized by NMR. P(HEMA‐co‐MAH) beads were characterized by swelling studies, FT‐IR spectroscopy, scanning electron microscopy (SEM) and elemental analysis. P(HEMA‐co‐MAH) affinity beads with a swelling ratio of 65% were used in the separation of human immunoglobulin G (HIgG) from aqueous solutions and human plasma. The maximum HIgG adsorption on the P(HEMA‐co‐MAH) adsorbents was observed at pH 7.4 for phosphate and at pH 6.0 for morpholinoethanesulfonic acid buffers. The HIgG adsorption onto the PHEMA adsorbents was negligible. Higher adsorption values (up to 46.5 mg·g^–1) were obtained when the P(HEMA‐co‐MAH) adsorbents were used in aqueous solutions. Much higher amounts of HIgG were adsorbed from human plasma (up to 73.8 mg·g^–1). Adsorption capacities of other blood proteins were obtained as 3.2 mg·g^–1 for fibrinogen and 4.6 mg·g^–1 for albumin. The total protein adsorption was determined to be 82.2 mg·g^–1. The pseudospecific affinity beads allowed one‐step separation of HIgG from human plasma. HIgG molecules could be repeatedly adsorbed and desorbed with these adsorbents without noticeable loss in their HIgG adsorption capacity.     

Purification of transferrin by magnetic immunoaffinity beads

Immunoaffinity adsorbent for transferrin (Tf) purification was prepared by immobilizing anti‐transferrin (Anti‐Tf) antibody on magnetic monosizepoly(glycidyl methacrylate) beads, which were synthesized by dispersion polymerization technique in the presence of Fe₃O₄nanopowder and obtained with an average size of 2.0 μm. The magnetic poly(glycidyl methacrylate) (mPGMA) beads were characterized by Fourier transform infrared spectroscopy, swelling tests, scanning electron microscopy, electron spin resonance spectroscopy, thermogravimetric analysis and zeta sizing analysis. The density and swelling ratio of the beads were 1.08 g/cm³ and 52%, respectively. Anti‐Tf molecules were covalently coupled through epoxy groups of mPGMA. Optimum binding of anti‐Tf was 2.0 mg/g. Optimum Tf binding from aqueous Tf solutions was determined as 1.65 mg/g at pH 6.0 and initial Tf concentration of 1.0 mg/mL. There was no remarkable loss in the Tf adsorption capacity of immunoaffinity beads after five adsorption–desorption cycles. Tf adsorption from artificial plasma was also investigated and the purity of the Tf molecules was shown with gel electrophoresis studies.     

Silica Meets Tannic Acid: Designing Green Nanoplatforms for Environment Preservation

Hybrid tannic acid-silica-based porous nanoparticles, TA-SiO₂ NPs, have been synthesized under mild conditions in the presence of green and renewable tannic acid biopolymer, a glycoside polymer of gallic acid present in a large part of plants. Tannic acid (TA) was exploited as both a structuring directing agent and green chelating site for heavy metal ions recovery from aqueous solutions. Particles morphologies and porosity were easily tuned by varying the TA initial amount. The sample produced with the largest TA amount showed a specific surface area an order of magnitude larger than silica nanoparticles. The adsorption performance was investigated by using TA-SiO₂ NPs as adsorbents for copper (II) ions from an aqueous solution. The effects of the initial Cu²⁺ ions concentration and the pH values on the adsorption capability were also investigated. The resulting TA-SiO₂ NPs exhibited a different adsorption behaviour towards Cu²⁺, which was demonstrated through different tests. The largest adsorption (i.e., ~50 wt% of the initial Cu²⁺ amount) was obtained with the more porous nanoplatforms bearing a higher final TA content. The TA-nanoplatforms, stable in pH value around neutral conditions, can be easily produced and their use would well comply with a green strategy to reduce wastewater pollution.     

Effect of pH on Competitive Adsorption of Cu(II), Ni(II), and Zn(II) from Water onto Chitosan Beads

The amounts of adsorption of Cu²⁺, Ni²⁺, and Zn²⁺ from single, binary, and tertiary nitrate solutions onto glutaraldehyde cross-linked chitosan beads were measured. The beads had an average particle size and pore volume of 2 mm and 0.06 cm³/g, respectively, and had a BET surface area of 60 m²/g. All experiments were performed at 298 K as a function of initial pH (2.0–5.0), total metal concentration (0.77–17.0 mol/m³), and molar concentration ratio (0.25–4) in the aqueous phase. It was shown that the amount of metal adsorption generally increased with increasing solution pH. Competitive adsorption was significant in binary and tertiary systems when Cu²⁺ was present. The selectivity factor reached maximum in an equilibrium pH range of 5.1–5.3 and 4.5–4.9 for the Cu-Ni and Cu-Zn binary systems, respectively. This adsorbent provided a possibility for selective separation of Cu²⁺ from such multi-component solutions.     

Preparation of poly(hydroxyethyl methacrylate-co-methacrylamidohistidine) beads and its design as a affinity adsorbent for Cu(II) removal from aqueous solutions

Different metal-complexing ligands carrying synthetic adsorbents have been reported in the literature for heavy metal removal. We have developed a novel and new approach to obtain high metal adsorption capacity utilizing 2-methacrylamidohistidine (MAH) as a metal-complexing ligand. MAH was synthesized by using methacrylochloride and histidine. Spherical beads with an average size of 150–200 μm were obtained by the radical suspension polymerization of MAH and 2-hydroxyethylmethacrylate (HEMA) conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, p(HEMA-co-MAH) beads had a specific surface area of 17.6 m² g⁻¹. Synthesized MAH monomer was characterized by NMR. p(HEMA-co-MAH) beads were characterized by swelling studies, FTIR and elemental analysis. These p(HEMA-co-MAH) affinity beads with a swelling ratio of 65%, and containing 1.6 mmol MAH g⁻¹ were used in the adsorption/desorption of copper(II) ions from metal solutions. Adsorption equilibria was achieved in ∼2 h. The maximum adsorption of Cu(II) ions onto pHEMA was ∼0.36 mg Cu(II) g⁻¹. The MAH incorporation significantly increased the Cu(II) adsorption capacity by chelate formation of Cu(II) ions with MAH molecules (122.7 mg Cu(II) g⁻¹), which was observed at pH 7.0. pH significantly affected the adsorption capacity of MAH incorporated beads. The observed adsorption order under non-competitive conditions was Cu(II)>Cr(III)>Hg(II)>Pb(II)>Cd(II) in molar basis. The chelating beads can be easily regenerated by 0.1 M HNO₃ with higher effectiveness. These features make p(HEMA-co-MAH) beads very good candidate for Cu(II) removal at high adsorption capacity.     

Suspension polymerization of poly(ethylene glycol) methacrylate: a route for swellable spherical gel beads with controlled hydrophilicity and functionality

 Spherical and swellable gel beads were obtained by the suspension polymerization of poly(ethylene glycol) methacrylate macromonomer (PEG-MA). The average size and size distribution properties, the equilibrium swelling behaviour and the protein adsorption characteristics of PEG-MA-based gel beads were determined. In the suspension polymerization system, the organic phase including monomer, cross-linker and diluent solution was dispersed in an aqueous medium by using poly(vinylpyrrolidone) as the stabilizer. The diluent solution was prepared by mixing cyclohexanol and octanol at different volume ratios. The suspension polymerization experiments were designed in two separate parts. In the first part, ethylene glycol dimethacrylate was selected as the cross-linker and swellable PEG-MA-based gel beads were obtained by changing the cross-linker concentration, the monomer/diluent ratio and the stirring rate. In the second part, a more hydrophobic structure, divinylbenzene (DVB) was tried as a cross-linker. In this part, PEG-MA-DVB copolymer beads were obtained by changing the DVB/PEG-MA feed ratio. Then, the hydrophicility of the resulting gel beads could be controlled by changing the feed ratio of hydrophilic macromonomer to hydrophobic cross-linker. This property was also used to control the extent of nonspecific protein adsorption onto the surface of the gel beads. The non specific albumin adsorption onto the gel beads decreased with increasing PEG-MA content. No significant nonspecific adsorption at the isoelectric point of albumin was detected onto the gel beads produced with the higher PEG-MA/DVB feed ratios. For specific albumin adsorption, a triazinyl dye (i.e., cibacron blue, CB F3G-A) was covalently attached onto the surface of the copolymer beads via terminal hydroxyl groups of PEG-MA. The results of albumin adsorption experiments with the CB F3G-A carrying beads indicated that an appreciable specific albumin adsorption capacity could be obtained with the gel beads produced with a PEG-MA/DVB feed ratio of 1.5/4.0. Received: 16 August 1999/Revised: 27 December 1999