Determination of the competitive adsorption of heavy metal ions on poly(n‐vinyl‐2‐pyrrolidone/acrylic acid) hydrogels by differential pulse polarography

Poly(N‐vinyl‐2‐pyrrolidone) and poly(N‐vinyl‐2‐pyrrolidone/acrylic acid) hydrogels were prepared by gamma irradiation for the removal of heavy metal ions (i.e., lead, copper, zinc, and cadmium) from aqueous solutions containing different amounts of these ions (2.5–10 mg/L) and at different pH values (1–13). The observed affinity order in adsorption of these metal ions on the hydrogels was Zn(II) > Pb(II) > Cu(II) > Cd(II) under competitive conditions. The optimal pH range for the heavy metal ions was from 7 to 9. The adsorption of the heavy metal ions decreased with increasing temperature in both water and synthetic seawater conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2013–2018, 2003     

Radiation synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone/acrylic acid) and poly(N‐vinyl‐2‐pyrrolidone/acrylamide) hydrogels for some metal‐ion separation

Two different hydrogels, prepared from N‐vinyl‐2‐pyrrolidone/acrylic acid (NVP/AAc) and N‐vinyl‐2‐pyrrolidone/acrylamide (NVP/AAm), were studied for the separation and extraction of some heavy‐metal ions from wastewater. The hydrogels were prepared by the γ‐radiation‐induced copolymerization of the aforementioned binary monomer mixtures. Further modification was carried out for the NVP/AAc copolymer through an alkaline treatment to improve the swelling behavior by the conversion of the carboxylic acid groups into its sodium salts. The thermal stability and swelling properties were also investigated as functions of the N‐vinyl‐2‐pyrrolidone content. The characterization and some selected properties of the prepared hydrogels were studied, and the possibility of their practical use in wastewater treatment for heavy metals such as Cu, Ni, Co, and Cr was investigated. The maximum uptake for a given metal was higher for a treated NVP/AAc hydrogel than for an untreated NVP/AAc hydrogel and was higher for an untreated NVP/AAc hydrogel than for an NVP/AAm hydrogel. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2642–2652, 2004     

The effect of gel composition on the uranyl ions adsorption capacity of poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) hydrogels prepared by gamma rays

Poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) (PVP‐g‐CA) hydrogels with varying compositions were prepared from ternary mixtures of N‐vinyl 2‐pyrrolidone–citric acid–water by using ⁶⁰Co γ‐rays. The effect of gel composition on the uranyl ions adsorption capacity of PVP‐g‐CA hydrogels was investigated. Uranyl adsorption capacity of these hydrogels were found to be in the range of 18–144 mg [UO]/g dry gel from the aqueous solution of uranyl nitrate and 22–156 mg [UO]/g dry gel from the aqueous solution of uranyl acetate, depending on the content of citric acid in the hydrogel, while poly(N‐vinyl 2‐pyrrolidone) hydrogel did not sorb any uranyl ion. The swelling of PVP‐g‐CA hydrogel containing 2.7 mol % CA was observed in water (1620%), in uranyl acetate solution (1450%) and in uranyl nitrate solution (1360%), as compared to 700% swelling of pure PVP hydrogels. The diffusion coefficients were varied from 12.57 up to 4.04 • 10⁻⁸ m² s⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1037–1043, 2000     

Competitive removal of Pb2+, Cd2+, and Zn2+ by poly(acrylamide‐co‐maleic acid) hydrogels/differential pulse polarographic determination

Poly(acrylamide‐co‐maleic acid) [P(AAm/MA)] hydrogels, with various compositions, were prepared from ternary mixtures of acrylamide (AAm)/maleic acid (MA)/water by using ⁶⁰Co γ‐rays. The effect of composition of these hydrogels, on the competitive removal of Pb²⁺, Cd²⁺, and Zn²⁺ ions from aqueous solution, was investigated. The hydrogel compositions and their adsorption behaviors were determined by use of differential pulse polarography, a very sensitive electroanalytical technique. It was observed that the external stimuli of pH, temperature, and ionic strength have an important role on the adsorption. The increments of MA content in P(AAm/MA) hydrogels caused a significant increase in the adsorption these ions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2401–2406, 2004     

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     

Removal of nitrite ions from aqueous solutions by poly(N,N‐dimethylamino ethylmethacrylate) hydrogels

Removal of nitrite ions from aqueous solutions by protonated poly(N,N‐dimethylamino ethylmethacrylate) hydrogels (P(DMAEMA)) was investigated. We have shown that polycationic and pendant secondary amine group containing P(DMAEMA) hydogels is very efficient and highly selective for the removal of nitrite ions from aqueous solutions at even in very high concentrations. Adsorption studies have shown that pH of the nitrite solution has influence on the nitrite ion uptake capacity of P(DMAEMA) hydrogels. The adsorption capacity of hydrogels had been increased up to 3100 mg NO/g dry gel, by changing pH of the solution. The results of the adsorption studies showed that the interaction between nitrite ions and quaternized amine groups agree with the Langmuir‐type isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6023–6027, 2006     

DNA adsorption on poly(N,N‐dimethylacrylamide)‐grafted chitosan hydrogels

In this study, poly(N,N‐dimethylacrylamide) grafted chitosan (PDMAAm‐g‐CT) hydrogels were prepared for deoxyribonucleic acid (DNA) adsorption. Instead of directly grafting the N,N‐dimethylacrylamide (DMAAm) monomer onto the chitosan (CT) chains, poly(N,N‐dimethylacrylamide) with carboxylic acid end group (PDMAAm‐COOH) was firstly synthesized by free‐radical polymerization using mercaptoacetic acid (MAAc) as the chain‐transfer agent and then grafted onto the CT having amino groups. The synthesis of PDMAAm‐COOH and its grafting onto the CT chains were confirmed by attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. From gel permeation chromatography measurements, the number‐average molecular weight (M _n) and polydispersity index of PDMAAm‐COOH were found as 2400 g/mol and 2.3, respectively. The PDMAAm‐g‐CT hydrogels were utilized as the adsorbents in DNA adsorption experiments conducted at +4°C in a trisEDTA solution of pH 7.4. The hydrogels produced with higher PDMAAm‐COOH content exhibited higher DNA adsorption capacity. The DNA adsorption capacity up to 4620 μg DNA/g dry gel could be achieved with the PDMAAm‐g‐CT hydrogels prepared in 80.0 wt % PDMAAm‐COOH feed concentration. This value is approximately seven times higher than that of CT alone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enantioselective esterification reaction using immobilized Candida rugosa lipase on poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) hydrogel

Lipase from Candida rugosa was immobilized on poly(N‐vinyl‐2‐pyrrolidone‐co‐styrene) hydrogel (poly‐(VP‐co‐ST)) with ethylene dimethacrylate and α,α'‐azoisobutyronitrile, which act as crosslinker and initiator, respectively. Three different compositions of monomers were used, namely VP(%):ST(%), 10:90, 50:50, and 70:30 (wt(%)/wt(%)). The immobilized lipases were used in the enantioselective esterification of (R,S)‐2‐(4‐chlorophenoxy)‐propanoic acid with n‐tetradecanol. The optimum reaction condition of the enantioselective esterification for the native lipase and the poly(VP‐co‐ST) hydrogel immobilized lipases was determined with respect to temperature, solvents, and initial water activity (a_w). The optimum temperature obtained was 40°C, with the poly(VP‐co‐ST) hydrogel immobilized lipase VP(%)/ST(%):10:90 showing the highest enantiomeric excess. In the solvent effect studies, the best solvents for high enantioselectivity were chloroform and carbon tetrachloride. In the a_w studies, optimum α_w for NL, VP(%):ST(%), 10:90, and 50:50 was 0.328, while for VP(%):ST(%), 70:30, it was 0.55. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3381–3386, 2004     

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     

Effect of pH,ionic strength,and temperature on uranyl ion adsorption by poly(N‐vinyl 2‐pyrrolidone‐g‐tartaric acid) hydrogels

Poly‐electrolyte N‐vinyl 2‐pyrrolidone‐g‐tartaric acid (PVP‐g‐TA) hydrogels with varying compositions were prepared in the form of rods from ternary mixtures of N‐vinyl 2‐pyrrolidone/tartaric acid/water. The effect of external stimuli, such as the solution pH, ionic strength, and temperature, on uranyl adsorption by these hydrogels was investigated. Uranyl adsorption capacities of the hydrogels were determined to be 53.2–72.2 (mg UO/g dry gel) at pH 1.8, and 35.3–60.7 (mg UO/g dry gel) at pH 3.8, depending on the amount of TA in the hydrogel. The adsorption studies have shown that the temperature and the ionic strength of the swelling solution also influence uranyl ion adsorption by PVP‐g‐TA hydrogels. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2219–2226, 2000     

Equilibrium adsorption isotherm and controlled release of antibiotic drug chloroamphenicol from poly(2‐vinyl pyridine/acrylic acid) hydrogels prepared by gamma radiation

High water sorption of 2‐vinyl pyridine (2‐VP)/acrylic acid (AAc) hydrogel were prepared by free‐radical polymerization in aqueous solution of 2‐VP with AAc as comonomer. The amount of ionic monomer (AAc), the irradiation dose of prepared hydrogel, the pH, and the concentration of drug play an important factor on loading, adsorption, and releasing of water‐soluble chloroamphenicol drug. As a result of dynamic swilling tests, the effect of relative content of AAc on the swelling showed that it allowed a non‐Fickian type of water diffusion. The adsorption of the drug onto (2‐VP/AAc) hydrogels was studied by Freundlish adsorption isotherm. The drug concentrations showed an influence on the adsorption of drug which increased with increasing AAc content. From Freundlish adsorption isotherm, the empirical constants, k and n, can be evaluated and showed the ability of hydrogel to be loaded by the drug and the affinity of the drug to be uptake onto the hydrogel respectively. FTIR, TGA, and SEM techniques were used to study the characterization of hydrogel (2‐VP/AAc). Additionally, the release of the drug loaded from hydrogel discs was studied microbiologically to show that hydrophilic structure of the hydrogel has an antimicrobial effect as a dehydration of cytoplasm and unbalance of the cell wall functions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Strontium(II) ion uptake on poly(N‐vinyl imidazole)‐based hydrogels

In this article, we report on the extraction of Sr(II) ions from aqueous solution with a series of poly(N‐vinyl imidazole)‐based hydrogels. The hydrogels were synthesized by the crosslinking of N‐vinyl imidazole with four different crosslinkers with γ rays as initiators. The well‐characterized hydrogels were used as Sr(II) sorbents. Sr(II) uptake was determined with a colorimetric method with Rose Bengal anionic dye. Scanning electron microscopy–energy‐dispersive spectroscopy analysis of the Sr(II)‐loaded polymers was recorded to ascertain the uptake of Sr(II) ions. The experimental adsorption values were analyzed with the Freundlich and Temkin equations, and the kinetics of adsorption were investigated with a pseudo‐second‐order sorption kinetic model. The results show that the equilibrium data fit well in the Freundlich isotherm and followed a pseudo‐second‐order kinetic model. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Antimicrobial poly(N‐vinyl‐2‐pyrrolidone‐alt‐maleic anhydride)/poly(ethylene imine) macrocomplexes

The antimicrobial polymer/polymer macrocomplexes were synthesized by radical alternating copolymerization of N‐vinyl‐2‐pyrrolidone with maleic anhydride [poly(VP‐alt‐MA)] with 2,2′‐azobis‐isobutyronitrile as an initiator at 65°C in dioxane solutions under nitrogen atmosphere, and interaction of prepared copolymer with poly(ethylene imine) (PEI) in aqueous solutions. The susceptibility of some Gram‐negative (Salmonella enteritidis and Escherichia coli) and Gram‐positive (Staphylococcus aureus and Listeria monocytogenes) bacteria to the alternating copolymer and its PEI macrocomplexes with different compositions in microbiological medium was studied using pour‐plate technique. All the studied polymers, containing biologically active moieties in the form of ionized cyclic amide, and macrobranched aliphatic amine groups and acid/amine complexed fragments, were more effective against L. monocytogenes than those for Gram‐positive S. aureus bacterium. This fact was explained by different surface layer structural architectures of biomacromolecules of tested bacteria. The resulting polymeric antimicrobial materials are expected to be used in various areas of medicine and food industry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5841–5847, 2006     

Radiation synthesis of poly(N‐vinylpyrrolidone‐co‐methacrylic acid) hydrogels and their usability in uranyl ion adsorption

In this study, N‐vinylpyrrolidone(VP)/methacrylic acid (MAA) mixtures have been prepared at three different mole percents which the methacrylic acid composition around 5, 10, and 15%. Poly(N‐vinylpyrrolidone‐co‐methacrylicacid) P(VP/MAA) hydrogels irradiated at 3.4 kGy have been used for swelling and diffusion studies in water and uranyl ion solutions. The influence of dose, pH, relative amounts of monomers in MAA/VP monomer mixtures on the swelling properties have been investigated. P(VP/MAA) hydrogels were swollen in distilled water at pH 7.0. P(VP/MAA)1 hydrogel containing 36% (mole percent) methacrylic acid showed the maximum percent swelling in water. Adsorption isotherms were constructed for uranyl ions and P(VP/MAA) hydrogel systems. It has been found that P(VP/MAA) hydrogels have very high uptake of the uranyl ions succesfully in water containing uranyl ions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of a poly(N‐vinyl‐2‐pyrrolidone)/poly (ethylene glycol) hydrogel membrane reinforced with methyl methacrylate‐grafted polypropylene fibers for possible use as wound dressing

A hydrogel is a polymeric material that exhibits the ability to swell in water and retains a significant fraction of water within its structure, but does not dissolve in water. One of the major problems in the application of these materials is their relatively poor mechanical strength, attributed to the high degree of hydration of the gel. This work was directed to the study of the interactions between hydrophobic and hydrophilized fibers, with the objective of optimization of the mechanical properties of poly(N‐vinyl‐2‐pyrrolidone) membranes. The membranes were prepared by electron‐beam irradiation of an aqueous polymer solution. A nonwoven cloth made of polypropylene matted fiber, grafted with methyl methacrylate, was employed as a reinforcement. The changes in the main properties of the membranes, such as the gel content, swelling characteristics, cytotoxicity, and mechanical behavior, were investigated. The results showed an increase of 800% in tensile strength, without changes in the swelling and cytotoxicity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 662–666, 2002     

Poly[(N‐isopropylacrylamide)‐co‐(itaconic acid)] hydrogels with poly(ethylene glycol)

The aim of the work reported here was to investigate temperature‐ and pH‐sensitive hydrogels of N‐isopropylacrylamide (NIPAM) and itaconic acid (IA) and their semi‐interpenetrating polymer networks (semi‐IPNs) with varying contents of poly(ethylene glycol) (PEG). The stimuli responsiveness, swelling behaviour and mechanical properties of the hydrogels and semi‐IPNs were studied in order to investigate the effect of various amounts of PEG. Pulsed‐gradient spin‐echo NMR experiments were carried out to investigate the diffusion process. The pH sensitivity increased with an increasing amount of PEG in the semi‐IPNs, while the overall rate of water uptake was diffusion‐controlled (n < 0.5). For certain PEG contents (5 and 10 wt%), the semi‐IPNs exhibited better mechanical properties than the poly(NIPAM‐co‐IA) copolymer. The calculated values of the self‐diffusion coefficients of water indicated facilitated diffusion of water through the system with increased amounts of PEG, while the self‐diffusion coefficients of a model compound, metoprolol tartrate, showed no significant dependence on the amount of PEG. According to the results obtained and compared to results reported in the literature, the investigated semi‐IPNs may have potential applications in the controlled release of macromolecular active agents such as proteins and peptides. Copyright © 2009 Society of Chemical Industry     

Synthesis,characterization, and swelling responses of poly(N‐isopropylacrylamide)‐ and hydroxypropyl cellulose‐based environmentally sensitive biphasic hydrogels

Thermosensitive networks based on hydroxypropyl cellulose and N‐isopropylacrylamide crosslinked with N,N‐methylene bisacrylamide were synthesized by a simultaneous gamma radiation technique. The network yield was optimized by the variation of reaction parameters such as the total radiation dose, concentration of crosslinker and monomer, and amount of water. The hydrogels had a biphasic structure and good mechanical strength, even in the fully swollen state, and could be synthesized in any shape and size. Volume transitions as a function of time and temperature were studied for these hydrogels in water, and the effects on swelling in different media such as 0.5N NaOH, 0.5N HCl, and 5% NaCl at the optimum time and temperature were also studied. The response of the hydrogels to these diverse changes in the swelling media was observed, and the volume transitions due to environmental changes in the hydrogels were not sharp and discontinuous as a maximum volume collapse occurred at a temperature higher than the reported lower critical solution temperature of 32.5°C for N‐isopropylacrylamide. These hydrogels were environmentally sensitive and responded to changes in their thermal and ionic environment and have potential applications in diverse fields such as drug delivery, enzyme technology, and environmental management. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 479–488, 2004     

Swelling behavior of thermoreversible poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels

Thermoresponsive hydrogels based on N‐isopropylacrylamide and N‐vinylimidazole were synthesized, and their swelling–deswelling behavior was studied as a function of the total monomer concentration. For copolymeric structures with better thermoresponsive properties with respect to poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels, these hydrogels were protonated with HCl and HNO₃, and the copolymer behaviors were compared with those of the unprotonated hydrogels. The temperature was changed from 4 to 70°C at fixed pHs and total ionic strengths. The equilibrium swelling ratio, dynamic swelling ratio, and dynamic deswelling ratio were evaluated for all the hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1619–1624, 2004     

Swelling and diffusion studies of poly(N‐isopropylacrylamide/itaconic acid) copolymeric hydrogels in water and aqueous solutions of drugs

N‐Isopropylacrylamide/itaconic acid hydrogels (NIPAAm/IA) containing different amounts of itaconic acid prepared by irradiating with γ‐radiation were used in experiments on swelling and diffusion of the model drugs methylene blue, lidocaine, and sildenafil citrate (VIAGRA). The NIPAAm/IA hydrogels containing 0–3 mol % itaconic acid irradiated at 48 kGy has been used for swelling and diffusion studies in water and aqueous solutions containing the above‐mentioned model drugs. For these hydrogels, swelling studies indicated that swelling increased with the following order: water > lidocaine > methylene blue > VIAGRA. Diffusions of water and the drugs within hydrogels were found to be non‐Fickian in character. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 911–915, 2004     

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