Synthesis and characterization of magnetic beads containing aminated fibrous surfaces for removal of Reactive Green 19 dye: kinetics and thermodynamic parameters

BACKGROUND: Poly(HEMA‐co‐MMA) beads were prepared from 2‐hydroxyethyl‐methacrylate (HEMA) and methylmethacrylate (MMA) in the presence of FeCl₃. Thermal co‐precipitation of Fe(III) ions containing beads with Fe(II) ions was carried out under alkaline conditions. The magnetic beads were grafted with poly(glycidylmethacrylate; p(GMA)), and the epoxy groups of the grafted p(GMA) brushes were converted into amino groups by reaction with ammonia. RESULTS: The magnetic beads were characterized by surface area measurement, electron spin resonance (ESR), Mössbauer spectroscopy and scanning electron microscopy (SEM). The maximum adsorption of Reactive Green‐19 (RG‐19) dye on the p(GMA) grafted and amine modified magnetic beads was around pH 3.0. The adsorption capacity of magnetic beads was 84.6 mg dye g^?1. The effects of adsorbent dosage, ionic strength and temperature have also been reported. Batch kinetic sorption experiments showed that a pseudo‐second‐order rate kinetic model was applicable. CONCLUSION: The p(GMA) grafted and amine modified magnetic beads (adsorbent) were expected to have the advantage of mobility of the grafted chains in the removal of acidic dyes from aqueous solutions. The magnetic beads have potential as an adsorbent for removal of pollutants under various experimental conditions without significant reduction in their initial adsorption capacity. Copyright © 2011 Society of Chemical Industry     

Adsorption of lanthanum by magnetic alginate‐chitosan gel beads

BACKGROUND: The risk of environmental pollution is aggravated by the increasing application of considerable amounts of rare earth elements in advanced materials. This paper reports the preparation of novel magnetic alginate–chitosan gel beads and their application for adsorption of lanthanum ions from aqueous solution. RESULTS: Stable magnetic alginate–chitosan gel beads with average diameter 0.85 ± 0.05 mm were prepared by loading iron oxide nanoparticles onto a combined alginate and chitosan absorbent. The performance of the prepared beads for the adsorption of lanthanum ions from aqueous solution was tested. It was found that various parameters, such as aqueous pH, contact time, metal ion concentration, ion strength and temperature, have an effect on the adsorption. Adsorption equilibrium was reached in 10 h and the maximum uptake capacity was 97.1 mg g^?1. From the analysis of pH, FTIR and XPS data, it is proposed that lanthanum adsorption proceeds through mechanisms of cation exchange, electrostatic interaction and surface complexation, with the oxygen atoms the main binding sites. In addition, lanthanum ions could be selectively separated from coexisting base metal ions such as Pb (II), Cd (II), Co (II), Ni (II) and Cu (II) in the aqueous solution. CONCLUSION: The prepared magnetic alginate–chitosan gel beads exhibit high uptake capacity and selectivity for lanthanum sorption, and thus can be used for adsorptive recovery of lanthanum from aqueous solutions. Copyright © 2010 Society of Chemical Industry     

Microporous polypropylene fibers containing fine particles of poly(styrene‐co‐divinylbenzene) or poly(glycidylmethacrylate‐co‐divinylbenzene)

Styrene‐divinylbenzene or glycidylmethacrylate‐divinyl‐benzene were copolymerized in powdery polypropylene suspended in water and the resultant polymer composites were blended with a definite amount of polypropylene. The products consisted of polypropylene and the fine particles of the copolymer, which were uniformly dispersed in polypropylene phase. These products were melt‐spun to prepare polypropylene fibers containing the fine particles and then the fibers were stretched to make the fibers microporous. Some properties were estimated: porosity, 1.6–19.7%; average pore size, 0.004–0.009 µm; and specific surface, 9–137 m²/g. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 722–727, 1999     

Evaluation of Adsorption Characteristics of Malachite Green onto Almond Shell (Prunus dulcis)

The potential usage of almond shell (P. dulcis), which is an agricultural waste product, in the removal of malachite green from aqueous solutions was evaluated with respect to various experimental parameters including contact time, initial malachite green concentration, temperature, adsorbent concentration, etc. The adsorption kinetics of malachite green fitted well the pseudo-second-order kinetic model. The monolayer adsorption capacity of almond shell was found to be 29.0 mg g^?1. The adsorption of malachite green onto almond shell increased with raising the temperature. From the experimental results, almond shell could be employed as a low cost and easily available adsorbent for removal of malachite green in wastewater treatment process.     

Adsorption of cationic dyes on poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine‐O, Azure‐I and Pyronin‐Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure‐I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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

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

Physicochemical Parameters of Cu(II) Ions Adsorption from Aqueous Solution by Magnetic-Poly(divinylbenzene-n-vinylimidazole) Microbeads

This study is aimed at the synthesis and characterization of the mesoporous magnetic-poly(divinylbenzene-1-vinylimidazole)[m-poly(DVB-VIM))microbeads(average diameter = 53–212 µm); their application as adsorbent in the removal of Cu(II) ions from aqueous solutions was investigated. The mesoporous m-poly(DVB-VIM) microbeads were prepared by copolymerizing of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The mesoporous m-poly(DVB-VIM) microbeads were characterized by N₂ adsorption/desorption isotherms, ESR, elemental analysis, scanning electron microscope (SEM), and swelling studies. At fixed solid/solution ratio the various factors affecting adsorption of Cu(II) ions from aqueous solutions such as pH, initial concentration, amount of mesoporousm-poly(DVB-VIM)) microbeads, contact time, and temperature were analyzed. Langmuir, Freundlich, and Dubinin-Radushkvich isotherms were used the model adsorption equilibrium data. The Langmuir isotherm model was the most adequate. The pseudo first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The experimental data fitted to pseudo second-order kinetic. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy changes. Morever, after the use in adsorption, the mesoporous m-poly(DVB-VIM) microbeads with paramagnetic property was separated via the applied magnetic force. These features make the mesoporous m-poly(DVB-VIM) microbeads a potential candidate for support of Cu(II) ions removal under magnetic field.     

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     

Removal of chromium (VI) from aqueous solutions using poly(4‐vinyl pyridine) beads

Sorption of hexavalent chromium ions from aqueous solution by poly 4‐vinyl pyridine [Poly(4‐VP)] was studied. The batch method was applied for adsorption processes. The effects of initial ion concentration, time, pH and temperature on adsorption were investigated. A treatment time of 60 min was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value for the process. The maximum adsorption performance was achieved at 86.7 mg g^?1 using 500 mg L^?1 Cr (VI) solutions. The process of adsorption of Cr (VI) was explained by Langmuir isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2865–2870, 2006     

Blood protein adsorption onto a polymeric biomaterial of polyethylene glycol and poly[(2‐hydroxyethyl methacrylate)‐co‐acrylonitrile] and evaluation of in vitro blood compatibility

A semi‐interpenetrating polymer network (semi‐IPN) of polyethylene glycol (PEG) and crosslinked poly[(2‐hydroxyethyl methacrylate)‐co‐acrylonitrile] was prepared and adsorption of bovine serum albumin (BSA) on the IPN surfaces was investigated. The dynamic nature of the adsorption process was studied, and the effects of various experimental factors such as pH and ionic strength on the adsorption isotherms of BSA were investigated. Various kinetic parameters, such as the adsorption coefficient, rate constant for adsorption and penetration rate constants, were calculated. For assessment of in vitro blood compatibility of the IPN surfaces, water sorption, blood clot formation tests and percent hemolysis measurements were performed. Copyright © 2004 Society of Chemical Industry     

Concanavalin A immobilized magnetic poly(glycidyl methacrylate) beads for antibody purification

Concanavalin A (Con A) immobilized magnetic poly(glycidyl methacrylate) (mPGMA) beads in monosize and spherical for (1.62 μm in diameter) were used for the purification of human immunoglobulin G (IgG) from human plasma. Con A was immobilized by covalent binding onto the mPGMA beads. The maximum IgG adsorption on the mPGMA-Con A beads was observed at pH 6.0. The nonspecific IgG adsorption onto the plain mPGMA beads was very low (0.22 mg/g). Scatchard analysis of the adsorption isotherm for IgG on mPGMA-Con A beads showed an affinity constant (K_a) of 1.39 × 10⁵ M⁻¹ and a theoretical maximum adsorption capacity of 109.1 mg/g. An apparent IgG adsorption capacity of 66.2 mg/g was observed under the experimental conditions. IgG adsorption capacity from human plasma was observed as 48.0 mg/g. The adsorption of human serum albumin from plasma was 2.0 mg/g. The total protein adsorption was determined to be 50.0 mg/g. IgG molecules could be repeatedly adsorbed and eluted with the mPGMA-Con A beads without noticeable loss in the IgG adsorption capacity. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Preparation of poly(acrylamide) grafted onto crosslinked poly (HEMA-MMA-EGDMA) beads for the removal of phenol

ABSTRACT

Poly(acrylamide) (PAAM) was grafted onto crosslinked poly(hydroxy ethyl methacrylate) (HEMA)-based beads for the removal of phenol from aqueous solution. A beaded polymer with a PAAM surface shell was prepared in two steps: synthesis of crosslinked poly (HEMA (50% mol) - MMA (40% mol) - EGDMA (10% mol)) terpolymers spherical beads (200–420 µm) (resin 1) via the suspension polymerization method; and the grafting of PAAM was carried out by redox initiation from hydroxyl groups on resin1 by using cerium (IV) ammonium nitrate as the initiator.

The resulting polymeric sorbent (resin 2) with about 82 wt.% grafted PAAM has been demonstrated to be efficient to remove phenol from water. Moreover, phenol sorption capacities of resin 1 and resin 2 were compared and sorption experiments were performed depending on the initial phenol concentration and pH. Kinetic measurements and models were studied for resin 1 and resin 2.     

Adsorption of bovine serum albumin protein onto amino‐containing thermosensitive core‐shell latexes

Adsorption of bovine serum albumin (BSA) onto positively charged core‐shell latex particles with a polystyrene core and a rich poly(N‐isopropylacrylamide) (NIPAM)) shell layer was investigated as a function of pH, ionic strength and temperature. Adsorption of BSA protein onto such cationic and thermosensitive particles was found negligible below the LCST of poly(NIPAM), whereas it was much higher above it. In addition, the pH and the salinity dependence of the adsorbed amount at the plateau reflected the role of electrostatic interactions. Protein adsorption behaviour was discussed by taking into account the changes in the interfacial properties of polymer particles (structure of the shell, hydrophilic–hydrophobic balance, charge density) versus temperature, suggesting that coulombic forces are mostly operating in this process. A desorption study showed that the BSA release efficiency was dependent upon the incubation time of the preliminary adsorbed step, and the effect of pH and ionic strength confirmed the contribution of electrostatic interactions. Copyright © 2004 Society of Chemical Industry     

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     

Adsorption of ammonium and nitrate ions by poly(N‐isopropylacrylamide) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) gel in different states

The adsorption of ammonium and nitrate by temperature‐stimulus‐responsive poly(N‐isopropylacrylamide) (NIPA) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) (NIPA‐CH) gel in different states was investigated. Both the NIPA gel and NIPA‐CH gel could adsorb ammonium and nitrate in a swollen state (swollen gel) and a swelling state (swelling gel), and they adsorbed ammonium more than nitrate. When the gels were shrinking (shrinking gel), they could adsorb a little ammonium from solution, but when the gels were in a shrunken state (shrunken gel), they hardly adsorbed ammonium. The adsorption of both ammonium and nitrate increased for the swelling NIPA gel in comparison with the swollen gel. The NIPA‐CH gel was the opposite in this respect. The difference in the amounts of adsorption of ammonium and nitrate by the swollen and swelling NIPA‐CH gels was more significant than that of the NIPA gels. It was suggested that ions such as ammonium and nitrate could not diffuse into the gels freely. The adsorption of ammonium and nitrate was affected not only by the phase transitions of the gels but also by the electrical charges. The experimental results for the adsorption of ammonium and nitrate during the volume changes of the gels imply that if the gels are applied to the immobilization of microorganisms, they may improve mass transfer between the immobilization matrix and bulk liquid under cyclic temperature changes and promote reactions of the immobilized microorganisms, especially the nitrification of nitrifying bacteria immobilized by the NIPA‐CH gel. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2367–2372, 2005     

Deposition of poly(diphenylamine‐co‐o‐chloroaniline) by pulse potentiostatic method: Growth equation and characterization

Electrochemical copolymerization of diphenylamine (DPA) with o‐chloroaniline (OCA) was performed in aqueous 4M sulfuric acid using the pulse potentiostatic method (PPSM). By employing the tunable parameters in PPSM, polymeric films were deposited under different conditions. Cyclic voltammetry was used for evaluating the characteristics of the deposited polymeric films. A suitable growth equation for the deposition of polymer, relating the charge associated for the film deposition and the pulse parameters in PPSM, was deduced. Various surface parameters are evaluated. The formation of copolymer during PPSM deposition was revealed through critical analysis of the results. The characteristic differences between the individual homopolymers, poly(diphenylamine) and poly(o‐chloroaniline) and the copolymer, poly(diphenylamine‐co‐o‐chloroaniline), were brought out. The copolymer was also synthesized through a chemical method and characterized through infrared and ultraviolet‐visible spectroscopic analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 389–397, 2003     

竹炭对苯酚吸附的热力学及动力学参数的研究

研究了竹炭对水相中苯酚吸附的动力学和热力学参数。动力学实验表明:竹炭对苯酚的吸附拟用准一级动力学处理。并测定不同粒径、不同温度下竹炭对苯酚吸附的表观速率常数及活化能。热力学研究表明:竹炭对苯酚的吸附符合 Langmuir 等温吸附方程。测得吸附热ΔH=-14.0 kJ/mol,说明竹炭对苯酚的吸附过程为放热过程,且ΔH<40 kJ/mol,表明吸附过程主要为物理吸附。同时测得吉布斯自由能ΔG<0,且受温度的影响不大,表明吸附质从溶液到吸附剂表面的吸附过程是自发过程。     

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