Synthesis,characterization, and application of amberlite XAD‐2‐ salicylic acid‐ iminodiacetic acid for lead removal from human plasma and environmental samples

A new chelating resin is prepared by coup‐ling Amberlite XAD‐2 with salicylic acid (SAL) through an azo spacer. Then the polymer support was coupled with iminodiacetic acid (IDA). The resulting sorbent has been characterized by FT‐IR, elemental analysis, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) and studied for the preconcentration and determination of trace Pb (II) ion from human biological fluid and environmental water samples. The optimum pH value for sorption of the metal ion was 5. The sorption capacity of functionalized resin is 67 mg g⁻¹. The chelating sorbent can be reused for 20 cycles of sorption–desorption without any significant change in sorption capacity. A recovery of 95% was obtained for the metal ion with 0.5M nitric acid as eluting agent. The profile of lead uptake on this sorbent reflects good accessibility of the chelating sites in the Amberlite XAD‐2‐SAL/IDA. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Pb (II) on modified resin were analyzed by Langmuir, Freundlich, Temkin, and Redlich‐Peterson models. Based on equili‐brium adsorption data the Langmuir, Freundlich, and Temkin constants were determined 0.428, 20.99, and 7 × 10⁻¹² at pH 5 and 20°C. The method was successfully applied for determination of lead ions in human plasma and sea water sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification and characterization of poly (ethylene terephthalate)‐grafted‐acrylic acid/acryl amide fiber for removal of lead from human plasma and environmental samples

A new fibrous adsorbent was prepared by grafting acrylic acid/acryl amide (AA/AAm) comonomers onto poly (ethylene terephthalate) (PET) fibers. The resulting sorbent has been characterized by Fourier transform infrared (FT‐IR), elemental analysis, thermogravimetric analysis (TGA), FT‐Raman, and scanning electron microscopy (SEM) and studied for the preconcentration and determination of trace Pb (II) ion from human biological fluid and environmental water samples. The optimum pH value for sorption of the metal ion was 8. The sorption capacity of functionalized resin is 44.1 mg g^?1. The chelating sorbent can be reused for 20 cycles of sorption–desorption without any significant change in sorption capacity. A recovery of 100.2% was obtained for the metal ion with 0.5M nitric acid as eluting agent. Effect of grafting yield, shaking time, shape of sorbent, and pH of the medium on adsorption of the metal ion were investigated. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Pb (II) on modified fiber were analyzed by Langmuir, Freundlich, Temkin, and Redlich‐Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.236, 10.544, and 9.497 at pH 8 and 20°C, respectively. The method was applied for lead ions determination from human plasma and sea water sample. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption isotherm and kinetic modeling of a novel procedure for physical modification of silica gel using aqueous solutions of 4,4′-(1,2-ethanediyldinitrilo)bis-(2-pentanone) for preconcentration of Ni(II) ion

ABSTRACT

Aqueous solutions of 4,4′-(1,2-ethanediyldinitrilo)bis-(2-pentanone) (EDDBP) have been used in a novel green procedure for the physical modification of silica gel (SG) for solid-phase extraction and preconcentration of Ni(II) ion. Optimization experiments were carried out at 301 ± 1 K by batch technique. The EDDBP-modified SG was characterized using X-ray Diffraction Spectroscopy (XRD) and Brunaeur-Emmett-Teller (BET) determinations. The adsorption isotherm and kinetic models indicated a physisorption process. The modified SG showed moderate to high adsorption capacity values for Ni(II) ion (~98% removal efficiency) at pH 8. A sorption mechanism for Ni(II) chelation with EDDBP-modified-SG was proposed. These results suggest the procedure has advantages.     

Synthesis of a novel chelating resin functionalized with β‐dicarbonyl units from a new monomer and its use for selective separation and preconcentration of some trace metals in water samples

A new chelating resin, poly(4‐ethoxy‐2,4‐dioxobutyl 2‐methylacrylate), functionalized with β‐dicarbonyl units derived from a newly synthesized monomer was prepared and characterized with molecular spectroscopic methods. The synthesized polymer was used for the separation and preconcentration of Mn(II), Co(II), Ni(II), Zn(II), and Pb(II) ions before their determination by flame atomic absorption spectrometry. The effects of different parameters, such as pH of sample solution, sample and eluent flow rates, volumes of sample and eluent, concentration and type of eluent, and matrix ions on quantitative recovery of the analytes were evaluated for optimal experimental conditions. The adsorption capacities of the chelating resin for cobalt(II) and nickel(II) were found to be 24.2 and 19.8 mg g^?1, respectively. Validation studies for the proposed method were performed using three certified reference materials, and the results obtained were agreed with those of the certified values. The proposed method was successfully applied to the analysis of water samples. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] brushes grafted onto siliceous support for preconcentration and determination of cobalt (II) in human plasma and environmental samples

A chelating matrix prepared by surface grafting of polymer containing a functional monomer, poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-methylacrylamide] (poly(AGE/IDA-co-DMAA) onto a modified silica. The silica surface was modified by silylation with 3-mercaptopropyltrimethoxysilane followed by graft polymerization. Monomer of allyl glycidyl ether-iminodiacetic acid was synthesized by reaction of allyl glycidyl ether with iminodiacetic acid. The chelating sorbent can be reused for 15 cycles of sorption-desorption without any significant change in sorption capacity. The profile of cobalt uptake on the sorbent reflects good accessibility of chelating sites in poly(AGE/IDA-co-DMAA)-grafted silica gel. The equilibrium adsorption data of Co(II) on modified sorbent were analyzed by Langmuir, Freundlich, Temkin and Redlich-Peterson models. The method was applied for cobalt ions determination in human plasma and sea water sample with satisfactory results.     

Adsorption of copper(II) and EDTA‐chelated copper(II) onto granular activated carbons

Waste streams generated by electroless copper plating in the printed circuit boards manufacturing industry often contain copper complexed by strong chelating agents such as EDTA. The consequence of metal complexation by chelating agents is that alternative treatment to chemical precipitation is often necessary to achieve the low metal concentrations required by increasingly stringent environmental regulations. This paper examines the feasibility of using activated carbon to remove EDTA‐chelated copper(II) species as well as free copper(II) ions from aqueous solution. The adsorption characteristics of copper(II) and EDTA‐chelated copper(II) on two granular activated carbons prepared from coal and coconut shell were evaluated. Adsorption equilibrium data of copper(II) on the two carbons corresponded well to the Langmuir model. The coconut shell‐based carbon exhibited a greater adsorption capacity for copper(II) than the coal‐based carbon under similar experimental conditions. Solution pH had a considerable influence on copper(II) adsorption by the two carbons. Low adsorption levels of copper(II) at pH 3 and high adsorption levels in the pH range of 4–6 were observed. However, a reverse adsorption trend was observed when the chelating agent EDTA was added to the copper(II) solution. Adsorption of EDTA‐chelated copper(II) by the two carbons was higher at pH 3 than at pH 6. The contrasting adsorption behaviour of copper(II) ions and EDTA‐chelated copper(II) species can be readily explained in terms of electrostatic interaction in that solution pH influences the surface charge of the carbons as well as the charge property of copper(II) ions and EDTA‐chelated copper(II) species. © 2000 Society of Chemical Industry     

Melamine‐based microporous polymer for highly efficient removal of copper(II) from aqueous solution

In this study, we investigated the ability of a melamine‐based microporous polymer network as an adsorbent for removal of copper(II) species from aqueous solutions. A designed Schiff based network (SNW) with high specific surface area was synthesized using melamine and terephthalaldehyde monomers at 180 °C for 3 days followed by a freeze‐drying process. The porous structure of the material was confirmed by SEM analysis and CO₂ adsorption/desorption studies at 77.3 K. The adsorption character of the SNW polymer for various metal salts, namely Pb(II), Fe(II), Hg(II), Zn(II), Ni(II) and Cd(II), was investigated and a specific sorption behaviour against Cu(II) salts was observed. The role of pH and contact time was examined and the highest adsorption capacity for Cu(II) was found as 92% with pH 3.5 at the end of 300 min. As evidenced by XRD and Fourier transform infrared spectral analysis, the sorption mechanism is attributed to the coordination system formed between amino groups in the porous structure and Cu(II) ions. Reusability of the system was also demonstrated by applying four cycles without any significant loss of activity. © 2016 Society of Chemical Industry     

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L ‐lactide) (PLLA) onto silica nanoparticle surface by ring‐opening polymerization of L‐lactide (LA) was investigated in the presence of an amidine base catalyst. The ring‐opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica‐NH₂) and an amidine base catalyst to give PLLA‐grafted silica, but not in the presence of untreated silica (silica‐OH). In the absence of the amidine base catalyst no ring‐opening polymerization of LA even in the presence of silica‐NH₂ and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring‐opening graft polymerization of LA from the surface of silica‐NH₂. In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA‐grafted silica was smaller than that of silica‐NH₂. Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLA‐grafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

水样中痕量铜的富集和测定的研究

铜离子与1-(2-吡啶偶氮)-2-萘酚(PAN)反应,生成疏水性的络合物,在助溶剂乙醇的作用下,被萃取到三氯甲烷相中,用分光光度法测定三氯甲烷相中的Cu2+-PAN,建立了析相富集-分光光度法测定水样中痕量铜的分析方法。对影响络合反应和相分离的各种条件进行了优化。在选择的实验条件下,铜的质量浓度在0.50～15μg/mL范围内与吸光度呈线性关系,相关系数为0.999 57,方法的检出限为0.089μg/mL,对铜浓度为5.0μg/mL的样品溶液进行7次平行测定,相对标准偏差为1.67%。该方法用于水样中铜的测定,回收率在95.6%～101.5%之间。     

Separation/Preconcentration of Zn(II), Cu(II), and Cd(II) by Saccharomyces carlsbergensis Immobilized on Silica Gel 60 in Various Samples

Abstract

This study presents a solid phase extraction procedure based on column biosorption of Zn(II), Cu(II), and Cd(II) ions on Saccharomyces carlsbergensis immobilized on silica gel 60. The analytes were determined by flame atomic absorption spectrometry (FAAS). The optimum conditions for the quantitative recovery of the analytes, including pH, amount of solid‐phase, eluent type and flow rate of sample solution were examined. The effect of interfering ions on the recovery of the analytes was also investigated. Under the optimum conditions, recoveries of Zn(II), Cu(II), and Cd(II) were 99±2%, 98±2%, and 100±2% at 95% confidence level, respectively for spiked water samples. The analytical detection limits for Zn(II), Cu(II), and Cd(II) were 1.14, 1.66, and 1.48 ng mL^?1, respectively. The validation of the method was checked by the analysis of standard reference material (Tea leaves GBW‐07605) and spiked water, samples. The proposed method was applied for the determination of analytes in green onion, parsley, dam water, lake water, and tap water samples. The analytes has been determined in real samples with relative error lower than 8% and relative standard deviation lower than 10%.     

Adsorption behavior of copper(II) ion from aqueous solution on methacrylic acid‐grafted poly(ethylene terephthalate) fibers

The adsorption behavior of methacrylic acid‐grafted poly(ethylene terephthalate) fibers was studied toward the copper(II) ion in aqueous solutions by a batch equilibriation technique. The influence of treatment time, temperature, pH of the solution, metal ion concentration, and graft yield were considered. One hour of adsorption time was found sufficient to reach adsorption equilibrium for the copper(II) ion. It was found that the adsorption isotherm of Cu(II) fits Langmuir‐type isotherms. The adsorption process is not affected by the temperature when treated with low ion concentration, but is remarkably decreased at a high ion concentration. The heat of adsorption value was calculated as 0.71 kcal/mol. It was found that the reactive fibers are stable and regenerable by acid without losing their activity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 766–772, 2000     

Studies on polycarbazole‐modified electrode and its applications in the development of solid‐state potassium and copper(II) ion sensors

Electrochemical synthesis of polycarbazole, having better stability and electrochromic activity, in dichloromethane containing 0.1 M tetrabutyl ammonium perchlorate (TBAP) is reported at 1.4 V versus Ag/AgCl. The electrochemistry based on cyclic voltammetric measurements in dichloromethane containing TBAP show redox behavior of the polymer associated to doping and de‐doping of ClO ion within the polymer interstices. The polycarbazole matrix obtained by the potentiostatic and potentiodynamic modes of electropolymerization is characterized based on scanning electron microscopy, differential calorimetry, and infrared spectroscopy. De‐doping of the polymer is studied by electrochemical reduction in TBAP‐free dichloromethane followed by incubation of the polymer film in 1 M aqueous KCl solution for 24 h. The open circuit potential (OCP) of doped and de‐doped polycarbazole modified electrode under the present experimental conditions is found to 462 and 19 mV, respectively, versus SCE in 0.1 M NH₄NO₃. The de‐doped polymer shows remarkable sensitivity and selective to Cu(II) ion compared to its sensitivity for Fe³⁺, Ni²⁺, Co²⁺, Pb²⁺, and Cu⁺ ions. A typical response of the de‐doped polymer electrode to Cu(II) ion is reported. On the other hand, ClO doped polymer is used in the development of solid‐state K⁺ ion sensors using dibenzo‐18‐crown‐6/valinomycin as a neutral carrier–based, plasticized poly vinyl chloride matrix membrane assembled over a polymer‐modified electrode. The doped polymer under this condition helps in maintaining charge stabilization across Pt/polymer and polymer/PVC interfaces. The lowest detection limit for the potassium ion sensor is 5 × 10⁻⁵ M with a slope of 58 mV/decade for valinomycin‐based sensor and 6.8 × 10⁻⁵ M with a slope of 54 mV for dibenzo‐18‐crown‐6 carriers with a wide linearity. The typical potentiometric results on the sensitivity, detection limits, and OCP to K⁺ ion recorded using present polymer are compared with the data recorded earlier using polyindole and a similar neutral carrier–based PVC membrane. A comparison on electrode kinetics of these two polymer‐modified electrodes also has been made using the data on Tafel plots to study the relative kinetic polarizability based on ion‐exchange currents. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1749–1759, 2000     

The effect of crosslinking on the adsorption behavior of copper (II) onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone)

The adsorption behavior of Cu(II) ions onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone), polymer I, and onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone) crosslinked with different amounts of divinylbenzene (DVB), polymers II, III, and IV, in aqueous solutions was investigated using batch adsorption experiments as a function of contact time, pH, and temperature. The amount of metal ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest uptake was achieved at pH 7.0 and by using perchlorate as an ionic strength adjuster for polymers I, II, III, and IV. Results revealed that the adsorption capacity (q_e and Q_m) of Cu(II) ions decreases with increasing crosslinking due to the decrease of chelation sites. In addition, the rate of adsorption (k₂) of Cu(II) ions decreases with the increase of crosslinking because it becomes more difficult for Cu(II) ions to diffuse into the chelation sites. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated. The experimental data of the adsorption process was found to correlate well with the Langmuir isotherm model. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization and use of acid‐activated montmorillonite‐illite type of clay for lead(II) removal

The natural local deposits of montmorillonite‐illite type of clay (MIC) were susceptible for acid activation. Raw clay was taken for experimentation, disintegrated on acid activation with sulfuric acid, which showed a particle size distribution. The montmorillonite and illite phases in the raw clay disappeared on acid activation and the activated clay, MIC(AA), showed with sodium‐aluminum‐silicate and beidellite phases apart from quartz (low) phase. The raw and acid‐activated clays were characterized using X‐ray powder diffractometry, X‐ray fluorescence, Fourier transform infrared spectrometry, and energy dispersive X‐ray, and their adsorption capacities were compared. When tested for adsorption of Pb(II) in aqueous solutions, the acid‐activated clay showed about 50% increased adsorption than raw clay. Sips adsorption isotherm and pseudo‐second‐order kinetic models were found to be best for the batch adsorption data. Kinetic studies showed the existence of film diffusion and intraparticle diffusion. A two‐stage batch adsorber was designed for the removal of Pb(II) from aqueous solutions. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

A procedure to synthesize poly(methyl methacrylate)‐grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N‐diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting “from”). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S_N2 mechanism. The study was performed with a Kieselgel® S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4‐(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT‐functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid‐state ¹³C and ²⁹Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and ¹H‐NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT‐functionalized Kieselgel® S used. Poly(methyl methacrylate)‐grafted silica microparticles bearing high length grafts ( about 100) were synthesized. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preconcentration and matrix elimination for the determination of Pb(II), Cd(II), Ni(II), and Co(II)by 8‐hydroxyquinoline anchored poly(styrene‐divinylbenzene) microbeads

Poly(styrene-divinylbenzene), PS-DVB, microbeads were modified with 8-hydroxyquinoline (8-HQ) following nitration, reduction of  NO₂ to NH₂, and conversion of NH₂ to diazonium salt. Characterization of pristine,  NO₂,  NH₂,  NN⁺Cl⁻, and 8-QH functional groups modified microbeads was made by Fourier transform-infrared spectrometry (FTIR) and porosimetry. Total reflectron-X-ray florescence spectrometer (TXRF) was used to test the affinity of the 8-HQ modified microbeads to toxic metal ions. 8-HQ-modified microbeads were used to examine the adsorption capacity, recovery, preconcentration, and the matrix elimination efficiency for Pb(II), Cd(II), Ni(II), and Co(II) ions as a function of changing pH, initial metal-ion concentrations, and also equilibrium adsorption time of the studied metal ions. Preconcentration factors for the studied toxic metal ions were found to be more than 500-fold and recovery between 93.8% and 100.6%. Ultratrace toxic metal-ion concentrations in sea water were determined easily by using modified microbeads. Reference sea-water sample was used for the validation of the method, and it was found that recovery, preconcentration, and the matrix elimination were performed perfectly. For the desorption of the toxic metal ions, 3M of HNO₃ was used and desorption ratio shown to be more than 96%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Removal of Fe(III) ions from dilute aqueous solutions by alginic acid‐enhanced ultrafiltration

The removal of Fe(III) ions from aqueous solutions was studied using membrane filtration. A water‐soluble polymer alginic acid (AA) was used to bind the metal ions, which was followed by batch ultrafiltration using poly(methyl methacrylate‐methacrylic acid) membranes modified with poly(ethylene glycol) (PMMA‐MA‐PEG). The complexation behavior of AA and the effect pH on the rejection of iron were investigated. Maximum recovery of 87.13% was obtained when the filtration was carried out in the presence of AA at pH 3.1. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1096–1101, 2000