Colorimetric sensing of metal ions by bis(spiropyran) podands: Towards naked-eye detection of alkaline earth metal ions

In order to develop a selective and sensitive colorimetric sensor for metal ions, a series of oligoether-linked bis(spiropyran) podands were prepared and their ability to colorimetrically sense alkaline earth metal ions was investigated. UV–vis absorption and ¹H NMR spectroscopic studies showed that the podands isomerized from the colorless spiropyran form to the colored merocyanine form upon complexation with alkaline earth metal ions, whereas spectral changes were not visible in the presence of alkali metal ions. Podands of spiropyran subunits linked by a spacer of a 3-oxapentan-1,5-dioxy group, i.e. X-BSP-1 (X = MeO, tBu, iPr, H, Cl, Br), exhibited high selectivity to Ca²⁺. Introduction of an electron-donating group to the 5-position of each indoline ring of the podand gave rise to an increase in affinity to alkaline earth metal ions, enhancing the sensitivity. The absorption maximum of the colored metal–X-BSP-1 complex varied over a range of ca. 30 nm, from reddish purple to bluish purple. Clear discrimination of the Ca²⁺ complex from that of Mg²⁺ was possible using the naked eye. These results indicate the potential application of the X-BSP-1 podands as a colorimetric sensor for Ca²⁺.     

Synthesis,complexation and biological effects studies of new thiacrown ethers derived quinoline: part I

A series of new thiacrown ethers derived quinoline 7–9 were synthesized in good yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Crowns 7 and 8 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Hg²⁺ and Zn²⁺ which begins to level off at a molar ratio of 1:1 crown to metal, indicating the formation of 1 stable 1:1 complex. On the other hand, crown 9 showed the formation of 1:1 complexes only with Ag⁺, Cu²⁺, Hg²⁺. The in vitro, a preliminary antimicrobial, antioxidant and cytotoxic effects on breast tumor cells were also reported. Five bacterial test strains were included in the present study. Antioxidant activity was measured in terms of the radical scavenging ability and decolorization of 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radicals. Cytotoxic effect of thiacrown was evaluated using MDA MB-231 cell line (human breast adenocarcinoma, ATCC HTB-26).     

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air–water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L², O₂S₂-thiacrown-ether L³, and O₂S₂-bridged thiacalixtube L⁴). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag⁺ and Hg²⁺ ions vs. other soft metal ions. In thioether L² and thiacalixtube L⁴, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag⁺ species) and the appearance of ligand-to-metal charge transfer bands at 330–340 nm (for Hg²⁺ species). Theoretical calculations for thioether L² and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag–thioether L² complexes and Hg–thiacalixtube L⁴ complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg²⁺) or sulfur atoms on the lower rim and bridging unit (Ag⁺). In thiacrown L³, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg²⁺ ion uptake by the Langmuir–Blodgett (LB) films of ligand L³ was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg²⁺ ions, which could be useful in the development of Hg²⁺-selective water purification systems or thin-film sensor devices.     

Physicochemical investigation of radiation‐grafted poly(acrylic acid)‐graft‐poly(tetrafluoroethylene–ethylene) copolymer membranes and their use in metal recovery from aqueous solution

ET‐g‐PAAc membranes were obtained by radiation grafting of acrylic acid onto poly(tetrafluoroethylene–ethylene) copolymer films using a mutual technique. The ion selectivity of the grafted membranes was determined toward K⁺, Ag⁺, Hg²⁺, Co²⁺, and Cu²⁺ in a mixed aqueous solution. The ion‐exchange capacity of the grafted membranes was measured by back titration and atomic absorption spectroscopy. The Hg²⁺ ion content of the membrane was more than that of either the K⁺ or Ag⁺ ions. The presence of metal ions in the membranes was studied by infrared and energy‐dispersive spectroscopy measurements. Scanning electron microscopy of the grafted and metal‐treated grafted membranes showed modification of the morphology of the surface due to the adsorption of K⁺ and Ag⁺ ions. No change was observed for the surface of the membrane that was treated with Hg²⁺ ions. The thermal stability of different membranes was improved more with Ag⁺ and Hg²⁺ ions than with K⁺ ions. It was found that the modified grafted membranes possessed good hydrophilicity, which may make them promising candidates for practical applications, such as for cation‐exchange membranes in the recovery of metals from an aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2692–2698, 2002     

Chromatographic Separations of Metal Ions on Zirconium Tungstoarsenate Impregnated Ion-Exchange Papers

Abstract

A new heteropolyacid salt ion-exchanger, zirconium tungstoarsenate, has been used for preparing impregnated ion-exchange papers. Twenty-nine metal ions have been chromatographed and R_F values determined in seven different mixed solvent systems containing 1-propanol and HNO³ or HCl. On the basis of the difference in selectivities for different metal ions on impregnated papers, a large number of binary and ternary separations has been obtained. Some of the important separations achieved are Ag⁺–Tl⁺, Ag⁺–Pt(IV), Zn²⁺–Hg²⁺, Sb³⁺–Bi³⁺, Zn²⁺–UO₂ ²⁺, Fe²⁺–Fe³⁺, Sb³⁺–Bi³⁺–Hg²⁺, Ag⁺–Ba²⁺–UO₂ ²⁺, and Ag⁺–Zn²⁺–Cu²⁺–Sn²⁺. The results are compared with those obtained on plain papers.     

Thioether‐Functionalized Corn Oil Biosorbents for the Removal of Mercury and Silver Ions from Aqueous Solutions

Heavy‐metal contamination is one of the most important environmental problems faced in the world, particularly in developing countries. Metals such as silver and mercury from drinking water, food, and air sources can accumulate in living organisms and present significant health concerns. Meanwhile, the demand for these metals in many industries continues to increase. In the present study, thioether‐functionalized corn oil (TFCO) from a photoinitiated thiol‐ene synthesis was utilized to remove Ag⁺ and Hg²⁺ ions from an aqueous solution. An aqueous solution containing AgNO₃ and Hg[NO₃]₂ was prepared and contacted directly with TFCO. After vortex mixing for 60 s, the experiment ran for 351 min with the aqueous phase being periodically sampled for the analysis of metal ions (M ⁿ⁺). Results showed that 88.9% of Ag⁺ and 99.6% of Hg²⁺ ions were removed from the aqueous phase by the TFCO. Mass balances indicated that the total M ⁿ⁺ concentration in the oil phase was 13.890 g kg^?1 under the conditions studied. TFCO exhibited higher selectivity for removing Hg²⁺ than for Ag⁺ ions. Analysis of the adsorption kinetics showed that a pseudosecond‐order model may be used to determine the rate of Ag⁺ ion sorption by the oil phase. The presence of the Hg²⁺ ions interfered with the adsorption of Ag⁺ ions from the aqueous solution.     

Synthesis and Metal‐ion Binding Properties of New N2S4O2‐ and N2S5O2‐Donor Macrocycles

Abstract

Synthetic procedures for new mixed‐donor macrocycle compounds were reported. The macrocyclic compounds were used in solvent extraction metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Pb²⁺, and Co²⁺. The metal picrate extractions were investigated at 25±0.1°C with the aid of UV‐visible spectrometry. It was found that 6,7,9,10,12,13,23,24‐octahydro‐19H,26Hdibenzo[h,t](1,4,7,13,16,22,10,19) dioxatetrathiadiazasiclotetracosine‐20,27(21H,28H)‐dione showed selectivity towards Ag⁺, Hg²⁺, and Cd²⁺ among the other metals. The extraction constants (Log K_ex) and complex compositions were determined for the Ag⁺ and Hg²⁺ complexes for this compound and 9,10,12,13,23,24,26,27,29,30‐decahydro‐5H,15H‐dibenzo‐[h,w][1,4,7,13,16,19,25‐,10,22] dioxapentathiadiazacycloheptacosine‐6,16(7H,17H)‐dione.     

Adsorption of metal cations on wool carbonising waste. Part 1. Adsorption isotherms

The adsorption of various metal ions (Hg²⁺, Ag⁺, Ni²⁺, Cr³⁺, Al³⁺, Zn²⁺ and Pb²⁺) on wool carbonising waste has been investigated to assess its possible use as an adsorbent in water pollution control. Isotherms show that few metal ions (Hg²⁺, Ag⁺ and Ni²⁺) are adsorbed satisfactorily by this material. Moreover, the adsorption capacity of the plant material within the carbonising waste is higher than that of the keratin fraction. Equations fitting the experimental data can be used for the design of processing units.     

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.     

Rhodamine-based fluorescent sensor for mercury in buffer solution and living cells

A novel fluorescent sensor based on thiooxorhodamine B has been prepared to detect Hg²⁺ in aqueous buffer solution. It demonstrates high selectivity for sensing Hg²⁺ with about 383-fold enhancement in fluorescence emission intensity and micromolar sensitivity (K_d = 7.5 × 10⁻⁶ mol L⁻¹) in comparison with alkali and alkaline earth metal ions (K⁺, Na⁺, Mg²⁺, Ca²⁺) and other transition metal ions (Mn²⁺, Ni²⁺, Co²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺, Pb²⁺, Cr³⁺, Fe³⁺). Meanwhile the distinct color changes and rapid switch-on fluorescence also provide ‘naked eyes’ detection for Hg²⁺ over a broad pH range. Moreover, such sensor is cell-permeable and can visualize the changes of intracellular mercury ions in living cells using fluorescence microscopy.     

Adsorption properties of novel chelating resins containing 2‐amino‐5‐methylthio‐1,3,4‐thiadizole and hydrophilic spacer arms for Hg2+ and Ag+

The adsorption properties, including the adsorption kinetics, adsorption isotherms, and adsorption selectivity, of newly formed chelating resins that contained a heterocyclic functional group and a hydrophilic spacer arm of poly(ethylene glycol) [polystyrene–diethylene glycol–2‐amino‐5‐methylthio‐1,3,4‐thiadizole (PS–DEG–AMTZ) and polystyrene–triethylene glycol–2‐amino‐5‐methylthio‐1,3,4‐thiadizole (PS–TEG–AMTZ)] were studied in detail. The results show that the adsorption kinetics of PS–DEG–AMTZ and PS–TEG–AMTZ for Hg²⁺ and Ag⁺ could be described by a pseudo‐second‐order rate equation. The introduction of a spacer arm between the polymeric matrix and functional group was beneficial for increasing the adsorption rates. The apparent activation energies of the resins for Hg²⁺ and Ag⁺ were within 20.89–32.32 kJ/mol. The Langmuir model could describe the isothermal process of Hg²⁺ and Ag⁺. The competitive adsorption of the resins for Hg²⁺ and Ag⁺ in binary mixture systems was also investigated. The results show that Hg²⁺ and Ag⁺ were adsorbed before the other metal ions, such as Cu²⁺, Zn²⁺, Fe³⁺, Cd²⁺, and Pb²⁺, under competitive conditions. Five adsorption–desorption cycles were conducted for the reuse of the resins. The results indicate that these two resins were suitable for reuse without considerable changes in the adsorption capacity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of the synthesis of chitosan derivatives containing benzo‐21‐crown‐7 and their adsorption properties for metal ions

Three new chitosan crown ethers, N‐Schiff base‐type chitosan crown ethers (I, III), and N‐secondary amino type chitosan crown ether (II) were prepared. N‐Schiff base‐type chitosan crown ethers (I, III) were synthesized by the reaction of 4′‐formylbenzo‐21‐crown‐7 with chitosan or crosslinked chitosan. N‐Secondary amino type chitosan‐crown ether (II) was prepared through the reaction of N‐Schiff base type chitosan crown ether (I) with sodium brohydride. Their structures were characterized by elemental analysis, infrared spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. In the infrared spectra, characteristic peaks of C?N stretch vibration appeared at 1636 cm^?1 for I and 1652 cm^?1 for II; characteristic peaks of N? H stretch vibration appeared at 1570 cm^?1 in II. The X‐ray diffraction analysis showed that the peaks at 2θ = 10° and 28° disappeared in chitosan derivatives I and III, respectively; the peak at 2θ = 10° disappeared and the peak at 2θ = 28° decreased in chitosan‐crown ether II; and the peak at 2θ = 20° decreased in all chitosan derivatives. In the solid‐state ¹³C NMR, characteristic aromatic carbon appeared at 129 ppm in all chitosan derivatives, and the characteristic peaks of carbon in C?N groups appeared at 151 ppm in chitosan crown ethers I and III. The adsorption and selectivity properties of I, II, and III for Pd²⁺, Au³⁺, Pt⁴⁺, Ag⁺, Cu²⁺, and Hg²⁺ were studied. Experimental results showed these adsorbents not only had good adsorption capacities for noble metal ions Pd²⁺, Au³⁺, Pt⁴⁺, and Ag⁺, but also high selectivity for the adsorption of Pd²⁺ with the coexistence of Cu²⁺ and Hg²⁺. Chitosan‐crown ether II only adsorbs Hg²⁺ and does not adsorbs Cu²⁺ in an aqueous system containing Pd²⁺, Cu²⁺, and Hg²⁺. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1886–1891, 2002     

Synthesis and adsorption properties of macroporous cross‐linked polystyrene that contains an immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole with tetraethylene glycol spacers

A novel chelating resin macroporous cross‐linked polystyrene immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole via a hydrophilic tetraethylene glycol spacer (PS‐TEG‐BMT) is synthesized and the structure is characterized by means of Fourier transform infrared spectroscopy (FTIR), energy dispersive X‐ray microanalysis (EDX), and elementary analysis. Its adsorption capacity for several metal ions such as Hg²⁺, Ag⁺, Ni²⁺, Pb²⁺, Cd²⁺, Fe³⁺, Bi³⁺, Zn²⁺, and Cu²⁺ are investigated. The initial experimental result shows that this resin has higher adsorption selectivity for Hg²⁺ and Ni²⁺ than for the other metal ions and the introduction of hydrophilic TEG spacer is beneficial to increase adsorption capacities. The result also shows that the Langmuir model is better than the Freundlich model to describe the isothermal process of PS‐TEG‐BME resin for Hg²⁺. Five adsorption‐desorption cycles demonstrate that this resin are suitable for reuse without considerable change in adsorption capacity. POLYM. ENG. SCI., 45:1515–1521, 2005. © 2005 Society of Plastics Engineers     

Response of Two-Dimensional Polymeric Cadmium Ferrocenyl Disulfonates to Heavy Metal Ions

A sandwich-like 2D infinite framework of {[Cd(pbbm)₂(SO₃FcSO₃)]·(CH₃OH)₂·(H₂O)₆} _n (1) with nanosized porous structure [Fc(SO₃)₂Na₂ = ferrocene-1,1′-disulphonate, pbbm = 1,1′-(1,3-propylene)-bis-1H-benzimidazole] was prepared by combining d ¹⁰ Cd²⁺ ions with highly conjugated pbbm and disodium ferrocene-1,1′-disulfonate. Experimental results show that 1 could serve as a new fluorescent probe for the detection of many divalent metal ions in water, such as Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Cd²⁺, Hg²⁺ and Pb²⁺, and trace organic solvents, including acetone, toluene, methylene chloride, ether, tetrahydrofuran, and methanol. The main product was very different from previous chemosensory materials that only identify one or two metal ions. The powdery multipurpose chemosensory materials proposed here could also sequester dangerous heavy metal ions, especially Pb²⁺. A computational study of ferrocene-1,1′-disulfonate and 1 gave insight into the process of ion exchange and sorption. This study introduces a promising new field of fluorescent chemosensors based on nanoporous coordination polymers with free functional groups.     

Preparation and adsorption behavior of macrocyclic tetra‐amine derivatives of chitosan

The new macrocyclic polyamine derivatives of chitosan were synthesized by reacting epoxy‐activated macrocyclic tetra‐amine with the C6 hydroxyl or C2 amino group in chitosan. The obtained copolymers (CTS‐OM, CTS‐NM) contain amino functional groups, the secondary amines, and more polar hydroxyl groups in its skeleton. Elemental analysis, infrared spectra, and solid‐state ¹³C‐NMR analysis confirmed their structures. The adsorption behavior of the macrocyclic polyamine grafted chitosan for Ag⁺, Pb²⁺, Hg²⁺, and Cr³⁺ was investigated. The experimental results showed that the two novel derivatives of chitosan have high adsorption capacity and good selectivity for some metal ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 407–412, 2005     

Rhodamine-based fluorescent sensor for mercury in buffer solution and living cells

A novel fluorescent sensor based on thiooxorhodamine B has been prepared to detect Hg²⁺ in aqueous buffer solution. It demonstrates high selectivity for sensing Hg²⁺ with about 383-fold enhancement in fluorescence emission intensity and micromolar sensitivity (K_d = 7.5 × 10⁻⁶ mol L⁻¹) in comparison with alkali and alkaline earth metal ions (K⁺, Na⁺, Mg²⁺, Ca²⁺) and other transition metal ions (Mn²⁺, Ni²⁺, Co²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺, Pb²⁺, Cr³⁺, Fe³⁺). Meanwhile the distinct color changes and rapid switch-on fluorescence also provide ‘naked eyes’ detection for Hg²⁺ over a broad pH range. Moreover, such sensor is cell-permeable and can visualize the changes of intracellular mercury ions in living cells using fluorescence microscopy.     

Cu2+ Selective Chromogenic Behavior of Calix[4]arene Derivative

This study involves the copper selective chromogenic response of 5, 11, 17, 23-Tetrakis (N-pyrrolidinomethyl)-25, 26, 27, 28-tetrahydroxycalix[4]arene based mannich base (3). Complexation ability of (3) was explored by examining the effect of a series of various metal ions, such as Li⁺, Na⁺, K⁺, Ag⁺, Ba²⁺, Ca²⁺, Mn²⁺, Mg²⁺, Sr²⁺, Ni²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Pb²⁺, Zn²⁺, Fe²⁺, Fe³⁺, and Al³⁺, by using UV-visible spectroscopy. Ligand (3) exhibited pronounced selectivity toward Cu²⁺ even in the presence of various co-existing ions. The stoichiometric analysis, i.e., Job's plot revealed that (3) form 1:1 complex with Cu²⁺ ion in DMF-H₂O system. The complexation phenomenon was confirmed by FT-IR spectroscopy that favors the selective nature of (3) with Cu²⁺.     

Spectrophotometric and electrochemical behavior of a novel azocalix[4]arene derivative as a highly selective chromogenic chemosensor for Cr

In this study, a novel azocalix[4]arene derivative, 5,11,17-tris[(1-naphtyl)azo]-25,26,27,28-tetrahydroxy-calix[4]arene (NAC4) bearing napthyl groups on the upper rim was synthesized. Its complexation behavior for alkali, alkaline-earth and various heavy metal ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Hg²⁺, Ni²⁺, Cd²⁺, Cu²⁺, Zn²⁺, Co²⁺, Fe²⁺, Cr³⁺, Ag⁺) was investigated by spectroscopic and voltammetric methods. This chemosensor exhibits decreased absorbance in the presence of Hg²⁺ and a unique absorbance quenching effect only for Cr³⁺. In addition, a new absorption band centered at 565 nm with the formation of the 1:1 host–guest complex (Cr³⁺-NAC4) was observed in the case of Cr³⁺, leading to an obvious color change from light orange to dark lilac. In voltammetric experiments, Cr³⁺ ions decreased voltammetric peaks of NAC4, whereas no significant changes occurred in the presence of the other metal ions. The Benesi–Hildebrand method was used to determine a logarithmic value of 3.76 for the association constant of the complex between Cr³⁺ and NAC4.     

Radiation Preparation of Conducting Nanocomposite Membrane Based on (Copper/Polyacrylic Acid/Poly Vinyl Alcohol) for Rapid Colorimetric Sensor of Mercury and Silver Ions

In this study, poly acrylic acid/poly vinyl alcohol capped copper as nanocomposite membrane Cu–(PAAc/PVA) has been prepared using gamma radiation. Aqueous solution of 0.2 mol Cu²⁺ ions chemically reduction using ascorbic acid and PAAc/PVA as stabilizer. Cu²⁺ ions could be deposited uniformly on the matrix network of PAAc/PVA membrane. The resulting Cu–(PAAc/PVA) nanocomposites membrane exhibited rapid colorimetric detection of mercury and silver ions associated with notable color changes of the membrane from yellow to pale gray and dark green, respectively. A novel label colorimetric sensor membrane Cu–(PAAc/PVA) has been developed for sensitive detection of Hg²⁺, Ag⁺ ions basis of the UV spectrophotometer data. A detection limit as low as 10^?5 and 10^?6 M of Hg²⁺ and Ag⁺ ions was achieved. This article proved that the Cu–(PAAc/PVA) nanocomposites membrane is exhibited excellent selectivity toward Hg²⁺, Ag⁺ ions. The advantages to the determination of Hg²⁺, Ag⁺ ions using Cu(PAAc/PVA) nanocomposite membrane is simple, low cost, rapid and easy observation by naked eye, the developed Cu–(PAAc/PVA) colorimetric membrane candidate for the detection of toxic Hg²⁺, Ag⁺ ions in environmental and biological samples. The particles size of synthesized Cu was performed using Transmission electron microscopy (TEM) indicates that Cu nanoparticles of size 8 nm are formed by green method. Absorption spectra of Cu nanoparticles deposited in PAAc/PVA at 591 nm confirm the capped of Cu nanoparticles inside PAAc/PVA matrices. The synthesized Cu nanocomposite has been found to be more AC conducting at low frequency than Hg and Ag nanoparticles. The increasing increase in conductivity of membrane can be correlated due to the formation of localized electronic states in polymer matrix due to insertion of Cu nanoparticles.     

Preparation and adsorption behavior for metal ions of cyclic polyamine derivative of chitosan

The new macrocyclic polyamine derivatives of chitosan were synthesized by reacting epoxy‐activated macrocyclic tetra‐amine with C6 hydroxyl or C2 amino group in chitosan. The obtained copolymers contain amino functional groups in its skeleton and secondary amines, and more polar hydroxyl groups. Elemental analysis, infrared spectra, and solid‐state ¹³C NMR analysis confirmed their structures. The adsorption behavior of the macrocyclic polyamine grafted chitosan for Ag⁺, Pb²⁺, Hg²⁺, and Cr³⁺ were investigated. The experimental results showed that the two novel derivatives of chitosan have high adsorption capacity and good selectivity for some metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3018–3023, 2006