Supported Liquid (SLM) and Polymer Inclusion (PIM) Membranes Pertraction of Copper(II) from Aqueous Nitrate Solutions by 1-Hexyl-2-Methylimidazole

The facilitated transport of Cu(II) ions from different aqueous nitrate source phases (c _Me = 0.001 M, pH = 6.0) across supported (SLMs) and polymer inclusion membranes (PIMs) doped with 1-hexyl-2-methylimidazole as ion carrier was reported. The membrane is characterized by means of atomic force microscopy (AFM). The results show that Cu²⁺ can be separated very effectively from other transition metal cations as Zn²⁺, Co²⁺, and Ni²⁺ from different equimolar mixtures of these ions. The highest initial fluxes of Cu(II) were found for PIM, while lower values were observed for SLM. However, after taking into account the morphology of the membranes (porosity, tortuosity), the values of the initial flux of Cu(II) transport across PIM is less than that across SLM. The recovery factor of Cu²⁺ ions during transport across PIM from different mixtures of cations is above 91% after 24 hrs and above 76% during transport across SLM. Also, the stability of PIM and SLM doped with 1-hexyl-2-methylimidazole was confirmed in replicate experiments.     

Controlled fabrication of multilayered 4-(pyrrole-1-yl) benzoate supported poly(3,4-ethylenedioxythiophene) linked hybrid films of Prussian blue type nickel hexacyanoferrate

The ability of 4-(pyrrole-1-yl) benzoic acid (PyBA) to form monolayer-type carboxylate-derivatized ultra-thin organic films on solid electrode surfaces was explored here to attract coordinatively and immobilize Ni²⁺ ions at the electrode/electrolyte interface. In the next step, the system was exposed to Fe(CN)₆³⁻ or Fe(CN)₆⁴⁻ solution to form a robust nickel hexacyanoferrate (NiHCF) layer. By repeated and alternate treatments in solutions of PyBA, Ni²⁺ cations, and Fe(CN)₆³⁻ or Fe(CN)₆⁴⁻ anions, the amount of the material could be increased systematically in a controlled fashion to form three-dimensional multilayered NiHCF-based assemblies. The layer-by-layer method was also extended to the growth of hybrid conducting polymer stabilized NiHCF films in which the initial PyBA-anchored NiHCF layer (formed on glassy carbon) was subsequently exposed (a desired number of times) through alternate immersions to the monomer (3,4-ethylenedioxythiophene), Fe(CN)₆³⁻ and Ni²⁺ solutions. During voltammetric potential cycling (electropolymerization) in the external supporting electrolyte solution, poly(3,4-ethylenedioxythiophene) or PEDOT linked NiHCF-based multilayered films were produced. They were characterized by good stability and high dynamics of charge transport.     

Copper (II) Ions into Polyphosphazenes: Solid-Like Solution Behavior

Reaction of Cu(BF₄)₂ salt with the polymer [NP(OC₆H₄C(O)C–OC₆H₅)₂] _n (1) in THF affords three new polymers gels containing varied copper (II) ions contents, (2), (3), and (4). The nature of the copper (II) ions in the gel (2)–(4) was examined by IR spectroscopy, solid state ³¹P, ¹³C and ⁶³Cu NMR spectroscopy and EPR spectroscopy. Despite the copper content, the gels were insulators as measured by complex impedance spectroscopy. SEM images show a uniform distribution of the Cu (II) ions and a most porous morphology than those without copper polymer. TEM images show the formation of small aggregates being smallest for, gel (2) of about 200 nm. All the data suggest the Cu²⁺ centers behave as a solid dilute into the polyphosphazenes.     

Synthesis of novel copper ion-selective material based on hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate)

A novel hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate) using a double-imprinting approach for the Cu²⁺ selective separation from aqueous medium was prepared. In the imprinting process, both Cu²⁺ ions and surfactant micelles (cetyltrimethylammonium bromide – CTAB) were employed as templates. The hierarchically imprinted organic polymer named (IIP-CTAB), single-imprinted (IIP-no CTAB) and non-imprinted (NIP-CTAB and NIP-no CTAB) polymers were characterized by SEM, FTIR, TG, elemental analysis and textural data from BET (Brunauer–Emmett–Teller) and BJH (Barrett–Joyner–Halenda). Compared to these materials, IIP-CTAB showed higher selectivity, specific surface area and adsorption capacity toward Cu²⁺ ions. Good selectivity for Cu²⁺ was obtained for the Cu²⁺/Cd²⁺, Cu²⁺/Zn²⁺ and Cu²⁺/Co²⁺ systems when IIP-CTAB was compared to the single-imprinted (IIP-no CTAB) and non double-imprinted polymer (NIP-CTAB), thereby confirming the improvement in the polymer selectivity due to double-imprinting effect. For adsorption kinetic data, the best fit was provided with the pseudo-second-order model for the four materials, thereby indicating the chemical nature of the Cu²⁺ adsorption process. Cu²⁺ adsorption under equilibrium was found to follow dual-site Langmuir–Freundlich model isotherm, thus suggesting the existence of adsorption sites with low and high binding energy on the adsorbent surface. From column experiments 600 adsorption–desorption cycles using 1.8 mol L⁻¹ HNO₃ as eluent confirmed the great recoverability of adsorbent. The synthesis approach here investigated has been found to be very attractive for the designing of organic ion imprinted polymer and can be expanded to the other polymers to improve performance of ion imprinted polymers in the field of solid phase extraction.     

Chelation properties of poly(β‐diketone) polymer and its oxime toward heavy metal ions

The chelation behavior of poly(β‐diketone), polymer I, and poly(β‐diketone) oxime, polymer II, toward the divalent metal ions, Cu²⁺, Zn²⁺, Ni²⁺, and Cd²⁺, and the trivalent lanthanide metal ions, La³⁺, Nd³⁺, Sm³⁺, Gd³⁺, and Tb³⁺ was investigated by a batch equilibration technique as a function of contact time, pH, and counter ion. Polymer II exhibited improved chelation characteristics toward lanthanide metal ions in comparison with polymer I and the metal‐ion uptake follows the order Tb³⁺ ≈ Gd³⁺ ≈ Sm³⁺ > Nd³⁺ ≈ La³⁺. On the other hand, polymer I showed relatively higher capacity than polymer II, toward the investigated divalent metal ions, where the metal‐ion uptake follows the order Cu²⁺ > Cd²⁺ ≈ Zn²⁺ > Ni²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Antimicrobial properties of co-doped tricalcium phosphates Ca3-2x(MˊMˊˊ)x(PO4)2 (M = Zn2+, Cu2+, Mn2+ and Sr2+)

The substituted (Ca²⁺/Cu²⁺), and co-substituted (Cu²⁺/Zn²⁺), (Cu²⁺/Sr²⁺), and (Sr²⁺/Mn²⁺) β-tricalcium phosphate (β-TCP)-based Ca_3-2x(MˊMˊˊ)_x(PO₄)₂ (M = Zn²⁺, Cu²⁺, Mn²⁺ and Sr²⁺) solid solutions have been synthesized using solid-state route. The powder X-ray diffraction study shows the formation of β-TCP-type structure as the main phase in all solid solutions. The crystal structures and chemical compositions were approved using Fourier-transform infrared (FT-IR) absorption spectra and energy-dispersive X-ray spectrometry (EDX) data, respectively. The unit cell parameters and volume of as-synthesized samples directly depend on the radius of the incorporated ions. The limits of the single-phase solid solutions were found based on the possible occupation of the crystal sites in β-TCP structure. For the divalent ions with small radii, such as Cu²⁺ or Zn²⁺, the limit composition was found as Ca_2.571Mˊ_0.429–xMˊˊ_x(PO₄)₂ for Mˊ and Mˊˊ – Cu²⁺ and Zn²⁺. The enlargement of the unit cell by incorporation of Sr²⁺ allows to extend the limit of solid solutions up to Ca_2.5Sr_0.5–xMˊ_x(PO₄)₂ for Mˊ – Cu²⁺ or Mn²⁺. The antibacterial properties were studied on 4 bacteria (S. aureus, P. aeruginosa, E. coli and E. faecalis) and 1 fungus (C. albicans). It has been showed that co-doped Ca_2.5Sr_0.25Cu_0.25(PO₄)₂ sample exhibits the highest antimicrobial activity resulting in 92%, 96% and 96% inhibition growth rate for S. aureus, P. aeruginosa and E. faecalis, respectively. The antimicrobial properties are strongly related to the occupation of the crystal sites in the β-TCP structure by doping ions.     

Selective and rapid uptake of Cu(II) by bis(benzimidazole) modified oxirane and thiirane resins

The benzimidazole containing ligand 1,3-bis(benzimidazol-2-yl)propylamine (bbpaH) was anchored onto poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate) (GMT) and onto the thiirane analogue of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (GME-S). Abbreviations of the modified polymers are GMT-bbpaH and GME-S-bbpaH. A multistep synthesis was applied in an attempt to increase the ligand concentration on the polymer GMT, This resulted in the resin GMT-bbpaH(ind) of which the solid state CP MAS ¹³C-NMR data showed that in this case only a monobenzimidazole was formed, i.e. only the 3-benzimidazole group was formed.Batch extraction capacities were determined for the chloride salts of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, Zn²⁺ and Ca²⁺ in the pH range 0.9–6.0 in buffered solutions at room temperature. All three resins show a high selectivity for Cu²⁺ under competitive conditions, with maximum ligand occupations of 54%, 64% and 27% for GMT-bbpaH, GME-S-bbpaH and GMT-bbpaH(ind), respectively. The resin GMT-bbpaH also takes up some Zn²⁺ ions at pH > 4.5, the maximum ligand occupation being 17%. The resin GME-S-bbpaH shows some affinity for Zn²⁺ and Cd²⁺ ions in this pH range, with ligand occupations of 17% and 7%, respectively. Only GMT-bbpaH(ind) shows complete selectivity for Cu(II) at pH > 3, although the maximum Cu²⁺-uptake capacity is rather low.Kinetic experiments showed that the oxirane derivative exhibits a faster uptake kinetics compared with the thiirane analogue. Incomplete stripping of the Cu(II)-loaded ion-exchange resins and loss of Cu(II)-uptake capacity was observed during the regeneration experiments.     

Removal of Ag(l), Cu(II) and Zn(ll) ions with a supported liquid membrane containing cryptands as carriers

The interface behaviour in the facilitated co-transport of Ag(I), Cu(II) and Zn(II) ions through supported liquid membranes (SLMs) made of a flat-sheet polypropylene membrane support containing cryptands (2.2.2 or 2.2.1) as carriers was studied. The liquid-liquid extraction tests showed a maximum distribution coefficient when the carrier concentration was greaterthan 10⁻⁴M. In transport experiments the transmembrane flux increased with increasing carrier concentration reaching a limiting value at greater than 10⁻³M concentration. The calculation ofthe diffusion coefficients in membranes showed ahigherdiffusivityof2.2.2-metal complexes with respect to 2.2.1-metal complexes for silver ions. A sequence of diffusivity D(Ag+)>D(Cu²⁺)>D(Zn²⁺) was obtained, but carrier 2.2.1 showed a higher selectivity through copper ions. A sequence of diffusivity D(Cu²⁺)>D(Zn²⁺)>D(Ag⁺) was obtained. The diffusivity was significantly higher when using Celgard 2500 support compared to Celgard 2400 or 2402. Variable metal ion concentrations in the feed phase fluxes almost zero, at less than 10⁻² M concentration, were obtained. In the transient state of the transport through the SLM, different molar flow rates at the feed-membrane and membrane-strip interfaces were observed. The selectivity of the interfaces containing 2.2.2 in the separation binary mixtures of ions showed the following separation factors: SF_AgZn = 2.50, SF_AgCu = 1.64, SF_cuZn = 1.42.     

Behaviour of poly(ethylene glycol) during electrodeposition of bright copper coatings in sulfuric acid electrolytes

The interaction of poly(ethylene glycol) M _n= 3000 with copper I and II ions in aqueous-acidic media was studied by investigation of the specific electrical conductivity, optical density and the cyclic voltamperometric curves in Cu⁺ and Cu²⁺ solutions. The results suggest the formation of complexes of the {Cu⁺(-EO-)₃(x – 1)H₂O} and {Cu²⁺(-EO-)₄.(y – 1)(H₂O)₂} types. In the case when {–CH₂CH₂-O-} _n and Cl^– are simultaneously present in the copper electrolyte, the possibility of simultaneous complex formation between both copper ions and ethylene oxide units, and copper ions and chloride ions is considered. The strong increase in copper electrodeposition over-potential after the addition of polyethers to the electrolytes containing brighteners is explained by the formation of these complexes.     

Cuprous delafossites,Cu3(MFeSb)O6 (M = Na,Li) with honeycomb arrays,realized by topochemical ion-exchange reactions

The current work describes the synthesis, structure, magnetic and optical properties of Cu¹⁺ based delafossite oxides, Cu₃(MFeSb)O₆ (M = Na, Li) synthesized by the topotactic ion-exchange reactions (around 400 °C) of CuCl with Na₄FeSbO₆ and Na₃LiFeSbO₆ in an inert argon atmosphere. The synthetic procedure is significant as the oxides could not be synthesized by the solid state methods. Chemical analysis coupled with energy dispersive spectral analysis confirmed the extent of replacement of Na⁺ ions by Cu⁺ ions. A complete exchange of alkali metal ion, Na⁺ by Cu¹⁺ in the interlayers of these honeycomb oxides has been achieved using a ratio of 1:3 between Na₄FeSbO₆ and CuCl. An additional exchange of approximately 70 % Na⁺ ions from the honeycomb arrays is possible by varying the ratio to 1:4. Rietveld refinements (space group C2/c) of the powder X-ray diffraction data have been carried out to ascertain the phase purity and to verify the structure formed by edge shared honeycomb arrays separated by Cu¹⁺ in dumbbell configuration (O–Cu¹⁺-O). X-ray photoelectron spectroscopy analysis confirmed the oxidation states of the constituent ions, specifically copper as Cu¹⁺. A similar method is adopted to synthesize Cu₃(LiFeSb)O₆ by reacting Na₃(LiFeSb)O₆ and CuCl in the ratio 1:3 at 400 °C. These new delafossite oxides, Cu₃(MFeSb)O₆ (M = Na, Li) and Cu₃((Cu_0.7Na_0.3)FeSb)O_6, exhibit interesting magnetic properties which are significantly different from the rock salt based parent sodium analogs. Dominant antiferromagnetic interactions with a specific ordering temperature have been observed for these samples containing Fe³⁺ (d⁵) ions in the honeycomb. UV–visible diffuse reflectance measurements indicated the decrease in the band gap of Cu¹⁺ based oxides. This study highlights the importance of low temperature ion-exchange reactions as an effective route to stabilize multifunctional materials of potential importance for various applications.     

Osmium(VIII) catalyzed oxidation of a sulfur containing amino acid—a kinetics and mechanistic approach

The kinetics of osmium (VIII) catalyzed oxidation of DL-methionine by hexacyanoferrate(III) (HCF) in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm^?3 was studied spectrophoto-metrically. The reaction between hexacyanoferrate(III) and DL-methionine in alkaline medium exhibits 2:1 stoichiometry (2HCF:DL-methionine). The reaction is of first order each in [HCF] and [Os(VIII)], less than unit order in [alkali] and zero order for [DL-methionine]. The decrease in dielectric constant of the medium increases the rate of the reaction. The added products have no effect on the rate of reaction. The main products were identified by spot test. A free radical mechanism has been proposed. In a prior equilibrium step Os(VIII) binds to OH^? species to form a hydroxide species and reacts with [Fe(CN)₆]^3? in slow step to form an intermediate species(C₁). This reacts with a molecule of DL-methionine in a fast step to give the sulfur radical cation of methionine and yields the sulfoxide product by reacting with another molecule of [Fe(CN)₆]^3?. The rate constant of the slow step of the mechanism is calculated. The activation parameters with respect to slow step of the mechanism are evaluated and discussed.     

Influence of copper (II) on biomineralization of CaCO3 and preparation of micron pearl-like biomimetic CaCO3

In all the waters where mollusks can grow, a variety of metal ions abounds. Attention has focused, however, on the effects of K⁺, Na⁺ and Mg²⁺ on the biomineralization of nacre, and those of other metal ions have been relatively neglected. This paper investigated the effects of representative copper (II) on the biomineralization of CaCO₃ using egg white as the organic matrix. The effects of copper ion concentration, aging time and the combined actions of a high concentration of both egg white and Cu²⁺ on the morphology and crystal type of CaCO₃ were studied, and the action mechanism was analyzed. The results show that copper (II) can induce the formation of vaterite, promote the spheroidization of mineralized particles, distort and deform the lamellar structure, and affect the surface roughness. Mechanism analysis shows that the bending and twisting of the protein molecule chain caused by the biuret reaction of Cu²⁺ with egg-white protein is the primary reason for the effects of copper (II) on the morphology and crystal type of CaCO₃. On this basis, a micron pearl-like CaCO₃ with a spherical structure consisting of uniform lamellae about 350 nm thick was obtained by exploiting the combined actions of high concentrations of egg white and Cu²⁺.     

Synthesis,characterization, metal sorption,and biological activity of poly(N‐heterocylic acrylamide)

N‐heterocyclic acrylamide monomers were prepared and then transferred to the corresponding polymers to be used as an efficient chelating agent. Polymers reacted with metal nitrate salts (Cu²⁺, Pb²⁺_, Mg²⁺, Cd²⁺, Ni²⁺, Co²⁺_, Fe²⁺) at 150°C to give metal‐polymer complexes. The selectivity of the metal ions using prepared polymers from an aqueous mixture containing different metal ion sreflected that the polymer having thiazolyl moiety more selective than that containing imidazolyl or pyridinyl moieties. Ion selectivity of poly[N‐(benzo[d]thiazol‐2‐yl)acrylamide] showed higher selectivity to many ions e.g. Fe³⁺, Pb²⁺, Cd²⁺, Ni²⁺, and Cu²⁺. While, that of poly[N‐(pyridin‐4‐yl)acrylamide] is found to be high selective to Fe³⁺ and Cu²⁺ only. Energy dispersive spectroscopy measurements, morphology of the polymers and their metallopolymer complexes, thermal analysis and antimicrobial activity were studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42712.     

Cationic conjugated polyelectrolyte-based fluorometric detection of copper(II) ions in aqueous solution

A series of water-soluble cationic polyfluorene copolymer containing 2,2′-bipyridine moieties (PFP-P_1-3) in the backbone were designed and synthesized as the fluorescent probes for Cu²⁺ ions. In the absence of the Cu²⁺ ion, the PFP-P₂ exhibits strong fluorescence emission in aqueous solution. Upon adding the Cu²⁺ ion, the PFP-P₂ coordinates to Cu²⁺ ions through weak N?Cu interactions, and its fluorescence is efficiently quenched by the Cu²⁺ ion with a Stern-Volmer constant (K_sv) of 1.44 × 10⁷ M⁻¹. The new method has high sensitivity with a detection limit of 20 nM. The minor interference from other heavy metal ions clearly shows that the PFP-P₂ can be used as the Cu²⁺ ion probe with good selectivity.     

Synthesis and structural characterization of copper(II) coordination polymers with 1,1,2,2-tetra(pyrazol-1-yl)ethane

Reaction between 1,1,2,2-tetra(pyrazol-1-yl)ethane (Pz⁴) and copper(II) nitrate in ethanol at room temperature and in solvothermal conditions (90 °C) lead to coordination polymers of two different structures. A ribbon-like coordination polymer {Cu₂(μ₂-NO₃)₂(H₂O)₄ μ′₂-Pz⁴}_n was formed at room temperature in which nitrate ions bind the monomeric units, while Pz⁴ ligands are responsible for cross-linking of {Cu(μ-NO₃)} chains. At 90 °C linear 1D coordination polymer was formed, in which Pz⁴ ligands bridge copper ions that in addition bear two monodentate nitrate ions.     

Selective Transport of Copper(I,II), Cadmium(II), and Zinc(II) Ions through a Supported Liquid Membrane Containing Bathocuproine,Neocuproine, or Bathophenanthroline

Abstract

Some selective transport systems for heavy metallic ions through a supported liquid membrane (SLM) containing a 2,2′-dipyridyl derivative ligand, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline (bathocuproine), 2,9-dimethyl-1,10-phenanthro-line (neocuproine), or 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline), were investigated. The transport of copper(I, II), cadmium(II), zinc(II), lead(II), and cobalt(II) ions was accomplished with a halogen ion such as chloride, bromide, or iodide ion as a pairing ion species for any SLM. The ranking of the permeability of the metallic ions was Cu^+,2+, Zn²⁺, Cd²⁺ ? Pb²⁺, Co²⁺. When the oxidation-reduction potential gradient was used as a driving force for metallic ions, the transport of Cu⁺ ion was higher than those of Cd²⁺ and Zn²⁺ ions for any SLM containing bathocuproine, neocuproine, or bathophenanthroline. On the other hand, in the transport system which used the concentration gradient of pairing ion species, the permeability of the Cu²⁺ ion decreased whereas that of the Cd²⁺ ion increased. Moreover, it was found that the different selectivity for the transport of metallic ions is produced by using various pairing ion species.     

Selective separation of some heavy metals by poly(vinyl alcohol)‐grafted membranes

A poly(vinyl alcohol) membrane (PVA) was modified by radiation graft copolymerization of acrylic acid/styrene (AAc/Sty) comonomers. The Cu and Fe ion‐transport properties of these membranes were investigated using a diaphragm dialysis cell. In the feed solution containing CuCl₂ or a mixture of CuCl₂ and FeCl₃, the PVA‐g‐P(AAc/Sty) membranes showed high degrees of permselectivity toward Cu²⁺ rather than toward Fe³⁺. The permeation of Cu²⁺ ions through the membranes was found to increase with decrease in the grafting yield. However, as the content of Cu²⁺ ions in the Cu/Fe binary mixture feed solutions decreased, the rate and the amount of transported Cu²⁺ through the grafted membrane decreased, with no appreciable permselectivity toward Fe³⁺. When Fe²⁺ ions were used instead of Fe³⁺ ions in the feed solution containing Cu²⁺, the transport of both Cu²⁺ and Fe²⁺ through the membrane was observed. The rate of transport of Fe²⁺ was higher than that of Cu²⁺. In addition, it was found that the selective transport of ions was significantly influenced by the pH difference between both sides of the membranes. As the pH of the feed or the received solution decreased, both Cu²⁺ and Fe³⁺ passed through the membrane and were transported to the received solution. The role of carboxylic acid and the hydroxyl groups of the grafted membranes in the transportation process of ions is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 125–132, 2000     

One unexpected mixed-valence Cu(I,II)-cyanide coordination polymer in situ originating from the cleavage of acetonitrile

Solvothermal reaction of CuCl₂·2H₂O and 2-(4-pyridyl)benzimidazole (PyHBIm) in a acetonitrile-water mixed solvent afforded a mixture of [Cu^I₂Cu^II(CN)₂(PyHBIm)₂Cl₂]_n (1) and [Cu^II(PyH₂BIm)₂Cl₄] (2). Complex 1 is a mixed-valence 1D ribbon Cu(I,II)-cyanide coordination polymer. One Cu(II) center linearly links two Cu(I) ions via two μ₂-CN bridges. XPS spectrum and bond valence sum (BVS) analysis have confirmed the mixed-valence characteristics. Cu(II) ion adopts a centrosymmetric square-planar geometry surrounded by two cyanides and two pyridyl groups. Cu(I) ions adopt a trigonal geometry coordinated by cyanide, imidazole group and Cl⁻ anion. The cyanide ligand is in situ generated from the cleavage of acetonitrile solvent, which indicates that acetonitrile is an environmentally friend cyanating agent. The mechanism of acetonitrile in situ cleavage under solvothermal condition is explained. Complex 2 is a centrosymmetric mononuclear Cu(II) compound. Four equivalent Cl⁻ anions lie on the equatorial plane. The protonated PyH₂BIm⁺ cation as a monodentate ligand coordinates to Cu(II) center via pyridyl terminal.     

Thermal and radiation chemical stabilities of some polymers after Cu(II) build-up

The interaction of polyacrylic acid (PAA), polysodium acrylate (PAANa), polyacrylamide (PAM) and acrylic acid–acrylamide copolymer P(AM-AA) with copper sulphate was studied to evaluate the thermal and radiation chemical stabilities of the resultant polymers which contained increasing quantities of Cu^{2 +} . It was found that the efficiency of the polymers toward Cu^{2 +} interaction, as determined by XRF, follows the order P(AM-AA) > PAM > PAANa. PAA was inactive, and no Cu^{2 +} ions were detected. Generally, the results obtained from TGA and DSC reveal that there is an improvement in the thermal stability when Cu^{2 +} is incorporated into the polymer matrix, but the amount of Cu^{2 +} bound to the polymeric chains does not correlate with their relative thermal stability. The degree of crystallinity estimated by X-ray diffraction also increases as Cu^{2 +} is incorporated into the polymer. In addition to the thermal stability, the radiation chemical stability of polymer with accumulated Cu^{2 +} was found to be very high, so that the percentage of Cu^{2 +} released from the crosslinked polymers was zero at radiation doses of up to 500 kGy. © 1999 Society of Chemical Industry     

Nickel(II)‐imprinted monolithic columns for selective nickel recognition

Ni²⁺‐imprinted monolithic column was prepared for the removal of nickel ions from aqueous solutions. N‐Methacryloyl‐L ‐histidine was used as a complexing monomer for Ni²⁺ ions in the preparation of the Ni²⁺‐imprinted monolithic column. The Ni²⁺‐imprinted poly(hydroxyethyl methacrylate‐N‐methacryloyl‐L ‐histidine) (PHEMAH) monolithic column was synthesized by bulk polymerization. The template ion (Ni²⁺) was removed with a 4‐(2‐pyridylazo) resorcinol (PAR):NH₃? NH₄Cl solution. The water‐uptake ratio of the PHEMAH–Ni²⁺ monolith increased compared with PHEMAH because of the formation of nickel‐ion cavities in the polymer structure. The adsorption of Ni²⁺ ions on both the PHEMAH–Ni²⁺ and PHEMAH monoliths were studied. The maximum adsorption capacity was 0.211 mg/g for the PHEMAH–Ni²⁺ monolith. Fe³⁺, Cu²⁺, and Zn²⁺ ions were used as competitive species in the selectivity experiments. The PHEMAH–Ni²⁺ monolithic column was 268.8, 25.5, and 10.4 times more selective than the PHEMAH monolithic column for the Zn²⁺, Cu²⁺, and Fe³⁺ ions, respectively. The PHEMAH–Ni²⁺ monolithic column could be used repeatedly without a decrease in the Ni²⁺ adsorption capacity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010