A Novel Highly Copper(ll)-selective Chelating Ion Exchanger Based on Poly(Glycidyl Methacrylate-coethylene Dimethacrylate) Beads Modified with Aspartic Acid Derivative

Abstract

Anchoring the hydroxyaspartic acid onto poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) beads or epoxysuccinic acid onto ammoniummodified 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.     

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     

Gloss reduction and morphological properties of polycarbonate and poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) blends with SAN‐co‐GMA as a reactive compatibilizer

The gloss properties of the polycarbonate (PC)/poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) (MABS) blend with styrene‐acrylonitrile‐co‐glycidyl methacrylate (SAN‐co‐GMA) as a compatibilizing agent were investigated. For the PC/poly(MABS)/SAN‐co‐GMA (65/15/20, wt %) blend surface, the reduction of gloss level was observed most significantly when the GMA content was 0.1 wt %, compared with the blends with 0.05 wt % GMA or without GMA content. The gloss level of the PC/poly(MABS)/SAN‐co‐GMA (0.1 wt % GMA) blend surface was observed to be 35, which showed 65% lower than the PC/poly(MABS)/SAN‐co‐GMA blend without GMA content. The gloss reduction was most probably caused by the insoluble fractions of the PC/poly(MABS)/SAN‐co‐GMA blend that were formed by the reaction between the carboxylic acid group in poly(MABS) and epoxy group in SAN‐co‐GMA. The results of optical and transmission electron microscope analysis, spectroscopy study, and rheological properties supported the formation of insoluble structure of the PC/poly(MABS)/SAN‐co‐GMA blend when the GMA content was 0.1 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46450.     

Porous properties of poly(glycidyl methacrylate‐co‐trimethylolpropane trimethacrylate) resins synthesized by suspension polymerization

Porous copolymer beads of 2,3‐epoxypropyl methacrylate (glycidyl methacrylate, GMA) crosslinked with 2‐ethyl‐2‐(hydroxymethyl)‐propan‐1,3‐diol trimethacrylate (trimethylolpropane trimethacrylate, TRIM) were prepared with toluene and octan‐2‐one as porogens by suspension polymerization. With an increase in the ratio of porogen to monomer, the total pore volume of poly(GMA‐co‐TRIM) increases significantly, whereas the surface area hardly changes. The total pore volume also depends on the nature of the porogen, exhibiting a maximum at the larger GMA contents in the monomer mixture of 50% v/v with octan‐2‐one and of 60% v/v with toluene, compared to that at the GMA content of 25% v/v with a 9/1 v/v mixture of cyclohexanol and dodecan‐1‐ol [Verweij, P. D.; Sherrington, D. C. J Mater Chem 1991, 1 (3), 371]. The surface area decreases significantly with an increase in the ratio of GMA to TRIM, almost regardless of the nature of the porogen. The porous properties of poly(GMA‐co‐TRIM) was well explained on the basis of phase separation, particularly taking into account not only the solubility parameters of the resulting polymer network and porogen but also the rigidity of TRIM. The porous poly(GMA‐co‐TRIM) may be a promising polymer matrix of novel materials for separation of boron isotopes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2374–2381, 2002     

Immobilization of lipase on poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) hydrogel

Lipase from Candida rugosa was immobilized by entrapment while polymerizing a poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) [poly(VP‐co‐ST)] hydrogel using ethylene dimethacrylate (EDMA) as the crosslinking agent. The immobilized enzymes were used in the esterification reaction of oleic acid and butanol in hexane. The activities of the immobilized enzymes and the leaching ability of the enzyme from the support with respect to the different compositions of the hydrogels were investigated. The thermal, solvent, and storage stability of the immobilized lipases were also determined. The activities were relatively higher when the percent compositions of VP(%):ST(%) were 50:50 and 30:70. The lipase immobilized on VP(%):ST(%) 50:50 showed the highest thermal stability, while lipase immobilized on VP(%):ST(%) 30:70 exhibited the highest solvent stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1404–1409, 2001     

Preparation of Chelating Resins Containing a Pair of Neighboring Carboxylic Acid Groups and the Adsorption Characteristics for Heavy Metal Ions

Abstract

For the functional enhancement of chelating resins containing carboxylic acids, copolymer beads were prepared by suspension polymerization of styrene (St), methyl methacrylate (MMA), and divinylbenzene (DVB) in the presence of toluene as diluent. The phenyl rings of the beads were directly chloromethylated, and the carboxylic ester groups of the beads were converted into hydroxymethyl groups by reduction followed by chlorination to give chloromethyl groups, respectively. The chelating resins containing a pair of neighboring carboxylic acid groups (NCAGs) were obtained by the alkylation of chloromethyl groups in copolymer beads with diethyl malonate in the presence of sodium hydride followed by hydrolysis using aqueous alkali solution. Accordingly, the structural effects of the resins on the adsorption of heavy metal ions were investigated. Poly(St‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, and Cu²⁺, whereas poly(MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Cu²⁺, Cd²⁺, and Co²⁺. On the other hand, poly(St‐co‐MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, Co²⁺, and Cu²⁺: a synergistic effect on the adsorption of heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, and Co²⁺ was observed. The adsorption ability of poly(St‐co‐MMA‐co‐DVB)‐based chelating resin among three kinds of chelating resins was relatively good.     

Environmental responses of poly(N‐isopropylacrylamide‐co‐glycidyl methacrylate derivatized dextran) hydrogels

A series of intelligent hydrogels (poly(NIPA‐co‐GMA‐Dex)) were synthesized by copolymerization of N‐isopropylacrylamide (NIPA) and glycidyl methacrylate derivatized dextran (GMA‐Dex) in aqueous solution with different ratios. Their swelling behaviors at different temperatures and in different pH and ionic strengths, and their mechanical properties were studied. It has found that poly(NIPA‐co‐GMA‐Dex) hydrogels are temperature‐, pH‐, and ionic strength‐sensitive associated with the roles of the component PNIPA and GMA‐Dex, respectively. Most significantly, poly (NIPA‐co‐GMA‐Dex) hydrogels exhibit simultaneously good swelling properties and mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2435–2439, 2005     

Influence of silica nanoparticles functionalized with poly(butyl acrylate‐co‐glycidyl methacrylate)‐g‐diaminodiphenyl sulfone on the mechanical and thermal properties of bismaleimide nanocomposites

The silica nanoparticles functionalized with poly(butyl acrylate‐co‐glycidyl methacrylate)‐g‐diaminodiphenyl sulfone (P(BA‐co‐GMA)‐g‐DDS)) were prepared via atom transfer radical polymerization and ring open reaction, and characterized by Fourier transform infrared and X‐ray photoelectron spectroscopy. Subsequently, the influence of SiO₂ content on the mechanical and thermal properties for the bismaleimide (BMI) resin nanocomposites modified with pristine SiO₂ and SiO₂‐P(BA‐co‐GMA)‐g‐DDS) was investigated. It was found that SiO₂‐P(BA‐co‐GMA)‐g‐DDS) was more effective as a modifier than pristine SiO₂. The most significant improvement of the impact strength (+108.7%) and flexural strength (+64.5%) was obtained with SiO₂‐P(BA‐co‐GMA)‐g‐DDS) at 0.5 wt% content. Moreover, the thermal properties of nanocomposites were distinctly improved with the addition of functionalized SiO₂. The reasons for these changes were discussed in this article. POLYM. COMPOS., 34:2154–2159, 2013. © 2013 Society of Plastics Engineers     

Monodisperse‐porous N‐methyl‐D‐glucamine functionalized poly(vinylbenzyl chloride‐co‐divinylbenzene) beads as boron selective sorbent

To generate a new sorbent with high boron adsorption capacity, we synthesized monodisperse‐porous poly(vinylbenzyl chloride‐co‐divinylbenzene), poly(VBC‐co‐DVB), beads 8.5 μm in size by a new “modified seeded polymerization” technique. By using their chloromethyl functionality, the beads were derivatized by a simple, direct reaction with a boron‐selective ligand, N‐methyl‐D ‐glucamine (NMDG). The selection of poly(VBC‐co‐DVB) beads as a starting material allowed to obtain high boron sensitive‐ligand density on the beads depending on their high chloromethyl content. In the batch adsorption runs performed using NMDG‐attached poly(VBC‐co‐DVB) beads as sorbent, boron removal was efficiently performed in a wide pH range between 4 and 11. Quantitative boron removal was observed with the sorbent concentration of 4 g/L. In the same runs, plateau value of equilibrium adsorption isotherm was obtained as 14 mg boron/g beads. Relatively higher boron adsorption was explained by high ligand density and high specific surface area of the sorbent. Boron adsorption isotherms were analyzed using Langmuir and Freundlich models. In the kinetic runs performed for boron removal, the equilibrium was attained within 10 min at a value of 98%. The fast kinetic behavior was explained by the smaller particle size and enhanced porosity of the new sorbent. Infinite solution volume model and unreacted core model were used to evaluate boron adsorption onto the NMDG‐attached poly(VBC‐co‐DVB) beads. The results indicated that the adsorption process is controlled by the particle‐diffusion step. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of zwitterionic stationary phase based on hydrophilic non‐porous poly(glycidymethacrylate‐co‐ethylenedimethacrylate) beads and their application for fast separation of proteins

A new hydrophilic strong/strong type zwitterionic stationary phase for high performance liquid chromatography (HPLC) was synthesized by chemical modification of 3.0 μm non‐porous monodisperse poly(glycidylmethacrylate‐co‐ethylenedimethacrylate)(P_GMA/EDMA) beads in the following steps. First, the beads were reacted with hydrochloride to obtain chlorizated beads; second, chlorizated beads were reacted with dimethylamine to obtain ammoniated beads; third, ammoniated beads were reacted with 1,3‐propanesultone to obtain non‐porous hydrophilic zwitterionic stationary phase. The stationary phase was evaluated in detail to determine its ion‐exchange properties, separability, reproducibility, hydrophilicity, and the effect of column loading and pH on the separation and retention of proteins. The highest dynamic protein loading capacity of the synthesized zwitterionic packing for bovin serum albumin and Lys were 18.3 and 27.4 mg g^?1, respectively. The zwitterionic stationary phase was capable of separating two acidic and three basic proteins simultaneously in less than 2.5 min by the flow‐rates of 3.0 mL min^?1. The zwitterionic resin was also used for rapid separation and purification of recombinant human interferon‐r (rhIFN‐r) and human granulocyte colony‐stimulation factor (hG‐CSF) from the crude extract solution. The satisfactory results were obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Affinity adsorption of recombinant human interferon‐α on monosize dye‐affinity beads

Monosize, nonporous poly(glycidyl methacrylate) [poly(GMA)] beads were prepared by dispersion polymerization. Cibacron Blue F3GA was covalently attached onto the poly(GMA) beads for adsorption of recombinant interferon‐α (rHuIFN‐α). Monosize poly(GMA) beads were characterized by scanning electron microscopy. Dye‐carrying beads (1.73 mmol/g) were used in the adsorption–elution studies. The effect of initial concentration of rHuIFN‐α, pH, ionic strength, and temperature on the adsorption efficiency was studied in a batch system. Nonspecific adsorption of rHuIFN‐α on the beads was 0.78 mg/g. Dye attachment significantly increased the rHuIFN‐α adsorption up to 181.7 mg/g. Equilibrium adsorption of rHuIFN‐α onto the dye‐carrying beads increased with increasing temperature. Negative change in free energy (ΔG⁰ < 0) indicated that the adsorption was a thermodynamically favorable process. ΔS and ΔH values were 146.1 J/mol K and ?37.39 kJ/mol, respectively. Significant amount of the adsorbed rHuIFN‐α (up to 97.2%) was eluted in the elution medium containing 1.0M NaCl in 1 h. To determine the effects of adsorption conditions on possible conformational changes of rHuIFN‐α structure, fluorescence spectrophotometry was employed. We concluded that dye‐affinity beads can be applied for rHuIFN‐α adsorption without causing any significant conformational changes. Repeated adsorption–elution processes showed that these beads are suitable for rHuIFN‐α adsorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 975–981, 2007     

Synthesis,characterization, reactivity ratios by nuclear magnetic resonance spectroscopy,and application of (2,5‐Dichlorophenyl acrylate‐co‐glycidyl methacrylate) polymers as adhesives for the leather industry

2,5‐ Dichlorophenyl acrylate (DPA)‐co‐glycidyl methacrylate (GMA) polymers having five different compositions were synthesized in 1,4‐dioxane using benzoyl peroxide as a free‐radical initiator at 70 ± 0.5°C. Using ¹H‐NMR spectroscopy, the composition of the two monomers in the copolymers was calculated by comparing the integral values of the aromatic and aliphatic proton peaks. The reactivity ratios were calculated by Fineman–Ross (r₁ = 0.31 and r₂ = 1.08), Kelen–Tudos (r₁ = 0.40 and r₂ = 1.15), and extended Kelen–Tudos (r₁ = 0.39 and r₂ = 1.16) methods. The nonlinear error‐in‐variables model was used to compare the reactivity ratios. The copolymers were characterized by ¹H and proton decoupled ¹³C‐NMR spectroscopes. Gel permeation chromatography was performed for estimating the M_w and M_n and M_w/M_n of the poly(DPA) and copolymers (DPA‐co‐GMA: 09 : 91 and 50 : 50). Thermal stability of the homo‐ and copolymers was estimated using TGA [poly(DPA) > DPA‐co‐GMA (50 : 50) > DPA‐co‐GMA (09:91)], while DSC was utilized for determining the glass transition temperature. T_g increased with increased DPA content in the copolymer. The 50 : 50 mol % copolymer was chosen for curing with diethanolamine in chloroform. The cured resins were tested for the adhesive properties on leather at different temperatures (50, 90, 100, and 110°C). The resin cured at 50 °C exhibited a maximum peel strength of 1.6 N/mm, revealing a good adhesive behavior. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1167–1174, 2006     

Modification of bismaleimide resin by poly(ethylene phthalate‐co‐ethylene terephthalate), poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate), and poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)

Aromatic polyesters were prepared and used to improve the brittleness of bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane and o,o′‐diallyl bisphenol A (Matrimid 5292 A/B resin). The aromatic polyesters included PEPT [poly(ethylene phthalate‐co‐ethylene terephthalate)], with 50 mol % of terephthalate, PEPB [poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate)], with 50 mol % of 4,4′‐biphenyl dicarboxylate, and PEPN [poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)], with 50 mol % 2,6‐naphthalene dicarboxylate unit. The polyesters were effective modifiers for improving the brittleness of the bismaleimide resin. For example, inclusion of 15 wt % PEPT (MW = 9300) led to a 75% increase in fracture toughness, with retention in flexural properties and a slight loss of the glass‐transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism was assessed as it related to the morphological and dynamic viscoelastic behaviors of the modified bismaleimide resin system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2352–2367, 2001     

Compatibilization of polypropylene/ poly(3‐hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3‐hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene‐g‐maleic anhydride) (PP–MAH), poly (ethylene‐co‐methyl acrylate) [P(E–MA)], poly(ethylene‐co‐glycidyl methacrylate) [P(E–GMA)], and poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) [P(E–MA–GMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(E–MA–GMA) > P(E–MA) > P(E–GMA) > PP–MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

N‐acetyl‐D‐galactosamine‐specific lectin isolation from soyflour with poly(HPMA‐GMA) beads

Soybean lectin was purified from seeds of Glycine max L.Merrill SA88. Poly(hydroxypropyl methacrylate‐glycidyl methacrylate) [poly(HPMA‐GMA)] beads were used as an affinity matrix and N‐acetyl‐D ‐galactosamine (GalNAc) was used as an affinity ligand. Soybean lectin adsorption with GalNAc attached poly(HPMA‐GMA) beads from soybean lectin solution (in phosphate buffered saline) was 5.0 mg/g. Maximum adsorption capacity for soybean lectin from the soy flour extract was 26.0 mg/g. Elution of soybean lectin from adsorbent was accomplished by 0.5M galactose solution. Purity of soybean lectin was determined by SDS‐PAGE. It was observed that soybean lectin could be repeatedly adsorbed and desorbed with GalNAc‐attached poly(HPMA‐GMA) beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and antimicrobial activity of silver nanoparticles on poly(GMA‐co‐EGDMA) polymer support

Poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) (poly(GMA‐co‐EGDMA) macroporous copolymer decorated with silver nanoparticles was prepared by a modification of poly(GMA‐co‐EGDMA) in the reaction with arginine, and consequent reduction of silver ions with amino groups. The mercury intrusion porosimetry, transmission electron microscopy, X‐ray diffraction, UV–vis reflection spectroscopy, and inductively coupled plasma atomic emission measurements were used to characterize obtained composite. The coordination of silver nanoparticles to the poly(GMA‐co‐EGDMA) copolymer was studied using infrared spectroscopy. Time dependence and concentration dependence of the antimicrobial efficiency of composite were tested against Gram‐negative bacteria Escherichia coli , Gram‐positive bacteria Staphylococcus aureus , and fungus Candida albicans . The composite ensured maximum reduction of both bacteria, while the fungi reduction reached satisfactory 96.8%. Preliminary antimicrobial efficiency measurements using laboratory flow setup indicated potential applicability of composite for wastewater treatment. POLYM. COMPOS., 38:1206–1214, 2017. © 2015 Society of Plastics Engineers     

Cu(II)‐incorporated,histidine‐containing,magnetic‐metal‐complexing beads as specific sorbents for the metal chelate affinity of albumin

N‐Methacryloyl‐(L )‐histidine methyl ester (MAH) was synthesized from metharyloyl chloride and histidine. Spherical beads with an average size of 150–250 μm were obtained by the suspension polymerization of ethylene glycol dimethacrylate and MAH in an aqueous dispersion medium. Magnetic poly(ethylene glycol dimethacrylate‐co‐N‐Methacryloyl‐(L )‐histidine methyl ester) [m‐p(EGDMA‐co‐MAH)] microbeads were characterized with swelling tests, electron spin resonance, elemental analysis, and scanning electron microscopy. The specific surface area of the beads was 80.1 m²/g. m‐p(EGDMA‐co‐MAH) microbeads with a swelling ratio of 40.2% and 43.9 μmol of MAH/g were used for the adsorption of bovine serum albumin (BSA) in a batch system. The Cu(II) concentration was 4.1 μmol/g. The adsorption capacity of BSA on the Cu(II)‐incorporated beads was 19.2 mg of BSA/g. The BSA adsorption first increased with the BSA concentration and then reached a plateau, which was about 19.2 mg of BSA/g. The maximum adsorption was observed at pH 5.0, which was the isoelectric point of BSA. The BSA adsorption increased with decreasing temperature, and the maximum adsorption was achieved at 4°C. High desorption ratios (>90% of the adsorbed BSA) were achieved with 1.0M NaSCN (pH 8.0) in 30 min. The nonspecific adsorption of BSA onto the m‐p(EGDMA‐co‐MAH) beads was negligible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2669–2677, 2004     

Biodegradable amphiphiles of grafted poly(lactide) onto 2‐hydroxyethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers as drug carriers

This article describes the synthesis and characterization of 2‐hydroxylethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers, (HEMA‐co‐NVP), via free radical polymerization followed by grafting of poly(lactide) onto (HEMA‐co‐NVP) copolymers, via ring opening polymerization using tin octoate as a catalyst. The copolymers and the grafted copolymers (i.e., amphiphiles) were subjected to sustained release studies using salicylic acid, as a model drug. Characterization of the formed copolymers was performed using ¹H‐NMR, ¹³C‐NMR, FTIR, TGA, DSC, and SEM techniques. Derivative of TGA thermogram was used to determine %hydrophilicity and %hydrophobicity in the grafted and ungrafted copolymers. The SEM morphology revealed porous layers with crispy structure that were most likely due to the presence of poly(lactide) chains. At lower content of poly(lactide) moiety, grafted copolymers showed non‐Fickian diffusion release rate, whereas Fickian diffusion release rate at higher content of poly(lactide) was observed. The increase of poly(lactide) content (i.e., larger %hydrophobicity) in the copolymer increased the drug‐sustainability, due to the consistent but porous amphiphilic degradable structures that allow controllable release of drug in time interval. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

pH and thermo‐responsive poly(N‐isopropylacrylamide) copolymer grafted to poly(ethylene glycol)

pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by ¹H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013