Sodium polyacrylate as a binding agent in diffusive gradients in thin-films technique for the measurement of Cu and Cd in waters

An aqueous solution containing sodium polyacrylate (PA, 0.0030 M) was used in diffusive gradients in thin-films technique (DGT) to measure DGT-labile Cu²⁺ and Cd²⁺ concentrations. The DGT devices (PA DGT) were validated in four types of solutions, including synthetic river waters containing metal ions with or without complexing EDTA, natural river water (Hun River, Shenyang, China) spiked with Cu²⁺ and Cd²⁺, and an industrial wastewater (Shenyang, China). Results showed that only free metal ions were measured by PA DGT, recovery = 98.79% for Cu²⁺ and recovery = 97.80% for Cd²⁺ in solutions containing only free metal ions, recovery = 51.02% for Cu²⁺ and recovery = 51.92% for Cd²⁺ in solution with metal/EDTA molar ratio of 2:1 and recovery = 0 in solutions with metal/EDTA molar ratio of 1:1 and 1:2. These indicated that the complexes of Cu-EDTA and Cd-EDTA were DGT-inert or not DGT-labile. The DGT performance in spiked river water (recovery = 8.47% for Cu²⁺ and recovery = 27.48% for Cd²⁺) and in industrial wastewater (recovery = 14.16% for Cd²⁺) were also investigated. Conditional stability constants (log K) of PA-Cu and PA-Cd complexes were determined as 6.98 and 5.61, respectively, indicating strong interaction between PA and the metals.     

ABSORPTION OF METAL IONS AND SWELLING PROPERTIES OF POLY(ACRYLIC ACID-CO-ITACONIC ACID) HYDROGELS

Hydrogels of acrylic acid and itaconic acid has been synthesized with different monomers ratios. The swelling process of the different xerogels immersed in water and salt solutions has been studied. The swelling of hydrogels loaded with metal cations (Cu²⁺, Zn²⁺) was also investigated. The swelling process was monitored by the increase in the weight of hydrogel as a function of time. The absorption properties of metal ions were studied by using the hydrogel, and different concentrations of copper and zinc solutions (prepared from sulphate salts). The influence of pH on the absorption process was studied. For the absorption of metal ions, the amount of ions absorbed within the hydrogel can be calculated from the initial and equilibrium concentrations of the metal ions in aqueous phase, the weight of the hydrogel, and the volume of solution used. Metal absorption increased when pH, salt concentration in external solution and itaconic acid content is levelled.

The swelling isotherms which consisted of an initial fast increase levelled off asymptotically to the equilibrium swelling limit. The experimental data clearly suggest that our hydrogels follow a second-order kinetics for both cases (unload and metal loaded). The kinetics rate constant and the equilibrium water content, K, have been calculated for every monomer ratio from the experimental data according to the kinetics equation. Both magnitudes decreased as the itaconic acid content decreases in the xerogels.     

(Sodium Alginate/Acrylamide) Semi‐Interpenetrating Polymer Networks and their Usability on Removal of Lead,Cadmium, Nickel Ions

In this study, (sodium alginate (NaAlg)/acrylamide (AAm)) interpenetrating polymer networks (IPN) have been prepared at three different compositions, where the sodium alginate composition varies 1, 2, and 3% (w/v) in 50% (w/v) acrylamide solutions. These solutions have been irradiated with a ⁶⁰Co‐γ source at different doses. The percent conversion was determined gravimetrically and 100% gelation was achieved at the 10.0 kGy dose. The swelling results at pH 7.0 and 9.0 indicated that (NaAlg/AAm)3IPN hydrogel, containing 3% NaAlg showed maximum % swelling in water, with swelling increasing in the order of Ni²⁺>Cd²⁺>Pb²⁺. Diffusion in aqueous solutions of metal ions within (NaAlg/AAm)IPN hydrogels was found to be Fickian character. Diffusion coefficients of (NaAlg/AAm)IPN hydrogels in water and aqueous solutions of metal ions were calculated. The maximum weight loss temperature and half life temperature for NaAlg, PAAm, (NaAlg/AAm)IPN and (NaAlg/AAm)IPN‐metal ion systems were found from thermal analysis studies. In the adsorption experiments, the efficiency of (NaAlg/AAm)IPN hydrogels to adsorb nickel, cadmium and lead ions from water was studied. (NaAlg/AAm)IPN hydrogels showed different adsorption for different aqueous solution of metal ion at pH 7.0. Adsorption isotherms were constructed for the (NaAlg/AAm)IPN‐metal ion systems. S type adsorption in the Giles classification system was found.     

Hg- and Cu-selective fluoroionophoric behaviors of a dioxocyclam derivative bearing anthrylacetamide moieties

New dioxocyclam derivatives bearing two anthracene fluorophores were prepared, and their fluoroionophoric properties toward transition metal ions were investigated. Chemosensor 2 having anthrylacetamide moieties exhibited pronounced Hg²⁺- and Cu²⁺-selective fluoroionophoric properties in aqueous acetonitrile solution over other representative transition metal ions, as well as alkali and alkaline earth metal ions. Chemosensor 2 also exhibited Hg²⁺ and Cu²⁺ selectivity under competitive conditions in the presence of physiologically and environmentally important metal ions. The detection limits for the sensing of Hg²⁺ and Cu²⁺ ions were 7.8 × 10⁻⁶ and 1.5 × 10⁻⁶ M, respectively, in aqueous 95% acetonitrile solution.     

Copper and Nickel Removal from Aqueous Solutions Using New Chelating Poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid] Hydrogels

New poly[Acrylamide/N‐vinyl pyrrolidone/3‐(2‐hydroxyethyl carbamoyl)acrylic acid], poly [AAm/NVP/HECA], chelating hydrogels with different composition of HECA monomer have been prepared via free radical solution polymerization using N,N‐methylene bisacrylamide as a crosslinker. The hydrogels obtained were loaded with metal ions and characterized by FT‐IR spectroscopy, Scanning Electron Microscope (SEM) and Thermogravimatric analysis (TGA). The removal of Cu²⁺ and Ni²⁺ from aqueous solutions by the hydrogel was examined by a batch equilibrium method. The influence of treatment time, pH, initial concentration of the metal ions and HECA content in the feed compositions on the amount of adsorbed metal ions was studied. Swelling of the hydrogel was also carried out in distilled water and metal ion solutions. The removal of the metal ions followed the following order: Ni²⁺>Cu²⁺. The amount of metal ions removed increased with increasing HECA content in the feed composition, treatment time, pH of the medium and initial concentration of metal ions. The desorption of metal ions were carried out using 1 N HCl and 0.5 N H₂SO₄. The poly[AAm/NVP/HECA] hydrogels could be used many times without significantly decreasing their adsorption capacity.     

Highly selective colorimetric naked-eye Cu2+ detection using new bispyrazolone silver nanoparticle-based chemosensor

In this work, we have successfully developed novel silver nanoconjugates of pyrazolone analogue and screened its chemosensing potential in aqueous medium. Bispyrazolone silver nanoparticles (Bispyra-AgNPs) were synthesised and characterised through FTIR, UV-visible spectroscopy and atomic force microscopy. The sensing ability was explored towards Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Fe²⁺, Li⁺, Pb²⁺, La³⁺, Hg²⁺, Mg²⁺, Ni²⁺ and Ba²⁺ metal ions, respectively. Bispyra-AgNPs showed a highly quenching potential in selective recognition of Cu²⁺and colour of the solution immediately turned from yellow to purple, after the addition of Cu²⁺ in to the solution. The developed method also displayed a remarkable selectivity for Cu²⁺ over others interfering metal ions. The binding ratio and stoichiometry of host-guest complex was found to be 1:1 and determined by Job’s method. The propose method is facile and sensitive to detect Cu²⁺ with detection limit of 10 µM.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Synthesis and Chelating Properties of Polystyrene Supported Schiff Base (N,N′-disalicylidenepropylenetriamine) Resin Toward Some Divalent Metal Ions

A new polystyrene-supported Schiff base resin, N,N-bis(salicylidenepropylenetriamine)- aminomethyl polystyrene, has been synthesized through a reaction between the commercially available 4-chloromethyl polystyrene polymer and the Schiff base, N,N′-disalicylidenepropylenetriamine. The chelation behavior of this resin toward the divalent metal ions Cu^{2 +}, Ni^{2 +}, Zn^{2 +}, and Pb^{2 +} in aqueous solutions was investigated. Batch equilibration experiments were carried out as a function of contact time, pH, amount of metal-ion, polymer mass, and temperature. The amount of metal-ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS). Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Cu^{2 +} and that the metal-ion uptake follows the order: Cu^{2 +} > Zn ^{2 +} > Ni^{2 +} > Pb²⁺. The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed.     

Synthesis and characterization of a novel copolymer of glyoxal dihydrazone and glyoxal dihydrazone bis(dithiocarbamate) and application in heavy metal ion removal from water

We demonstrate synthesis of water insoluble, novel copolymer P_A1 from condensation of glyoxal dihydrazone and glyoxal dihydrazone bis(dithiocarbamate) monomers having high capacity to remove metal ions from aqueous solution. The presence of a high atomic percentage of nitrogen and sulfur atoms in P_A1 leads to strong ligating ability with metal ions. The monomers and the polymer have been characterized by FTIR, UV–Visible spectroscopy, CHNS elemental analysis, NMR, MALDI-MS, and TG/DTA. As a proof of concept, the P_A1 is tested for its ability to remove heavy metal ions Cu²⁺, Co²⁺, Fe²⁺, Ni²⁺, Mn²⁺, and CrO ₇ ^2? from aqueous solutions. P_A1 efficiently removed metals ions from the metal solutions. The highest absorption ability has been observed toward the iron salts where 0.969 g metal salt is absorbed by 1 g polymer. This study has implication for inexpensive and efficient polymer for purification of water.     

"Off-On" based fluorescent chemosensor for Cu2+ in aqueous media and living cells

A novel Cu²⁺-specific “off-on” fluorescent chemosensor of naphthalimide modified rhodamine B (naphthalimide modified rhodamine B chemosensor, NRC) was designed and synthesized, based on the equilibrium between the spirolactam (non-fluorescence) and the ring-opened amide (fluorescence). The chemosensor NRC showed high Cu²⁺-selective fluorescence enhancement over commonly coexistent metal ions or anions in neutral aqueous media. The limit of detection (LOD) based on 3 × δ_blank/k was obtained as low as 0.18 μM of Cu²⁺, as well as an excellent linearity of 0.05-4.5 μM (R = 0.999), indicating the chemosensor of high sensitivity and wide quantitation range. And also the coordination mode with 1:1 stoichiometry was proposed between NRC and Cu²⁺. In addition, the effects of pH, co-existing metal ions and anions, and the reversibility were investigated in detail. It was also demonstrated that the NRC could be used as an excellent “off-on” fluorescent chemosensor for the measurement of Cu²⁺ in living cells with satisfying results, which further displayed its valuable applications in biological systems.     

Synthesis of new benzimidazolium salts with tunable emission intensities and their application as fluorescent probes for Fe in pure aqueous media

A series of novel, water-soluble benzimidazolium salts with common ‘fluorophore–spacer–receptor’ PET design has been synthesized. Despite the common PET scaffold these benzimidazolium salts displayed diverse emission intensities in pure aqueous solutions. The observed emission intensities were found to be influenced by the functionalized alkyl side arms present on the benzimidazolium ring. These benzimidazolium salts were also found to act as selective sensors for Fe³⁺ ions over other metal ions like Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Al³⁺, Cr³⁺, Co²⁺, Ni²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ag⁺, Cu²⁺ and Hg²⁺ in pure aqueous media.     

Heavy metal ions removal by nano-sized spherical polymer brushes

Nano-sized spherical polymer brushes(SPBs) consisting of both a polystyrene(PS) core and a brush shell of poly(acrylic acid)(PAA), poly(N-acrylcysteamine)(PSH), or poly(N-acrylcysteamine-co-acrylic acid)(P(SH-co-AA)), were prepared by photo-emulsion polymerization. The core-shell structure was observed by dynamic light scattering and transmission electron microscopy. Due to the strengthened Donnan effect, the PAA brush can adsorb heavy metal ions. Effects of the contact time, thickness of PAA brush and pH value on the adsorption results were investigated. Due to the coordination between the mercapto groups and heavy metal ions as well as the electrostatic interactions, SPBs with mercapto groups are capable to remove heavy metal ions selectively from aqueous solutions. The order of adsorption capacity of the heavy metal ions by SPBs with mercapto groups is: Hg2+ ≈ Au3+ Pb2+ Cu2+ Ni2+. The adsorbed heavy metal ions can be eluted from SPB by aqueous HCl solution, and the SPBs can be recovered. After three regenerations the recovered SPBs still maintain their adsorption capacity.     

A new rhodamine-based dual chemosensor for Al and Cu

A new rhodamine B derivative bearing a hydrazone group has been designed and prepared. The synthesized colorimetric and fluorescent molecular chemosensor can be used as a dual probe, selectively detecting Al³⁺ and Cu²⁺ in acetonitrile solution by monitoring changes in the absorption and fluorescence spectral patterns. The results show that Al³⁺ ions can induce a greater fluorescence enhancement, while the addition of Cu²⁺ ions induces a strong UV–vis absorption enhancement with weak fluorescence. The limits of detection of Cu²⁺ and Al³⁺ were estimated to be 2.9 × 10⁻⁷ M and 8.3 × 10⁻⁹ M, respectively.     

Hydrogels Triggered by Metal Ions as Precursors of Network CuS for DNA Detection

The gelation behavior of lithocholate (LC^?) with different metal ions in water was investigated. The microstructures of hydrogels were determined to be three‐dimensional (3D) networks of fibrous aggregates. The formation of fibrils was speculated to be mainly driven by the coordination between carboxylate of LC^? and metal ions, accompanied by the assistance of noncovalent interactions such as electrostatic and hydrophobic interactions. The hydrogels, which can maintain the mechanical strength at higher temperature, exhibit thermal stability. Their gelation capability was enhanced with the increase in acidity. The hydrogels of LC^? and Cu²⁺ mixtures served as the precursors for producing network nanostructures of CuS nanoparticles. These new CuS networks exhibit high fluorescence quenching ability and can act as an effective fluorescent sensing platform for ssDNA detection.     

Determination of Hg on poly(vinylferrocenium) (PVF)-modified platinum electrode

A new surface based on poly(vinylferrocenium) (PVF⁺)-modified platinum electrode was developed for determination of Hg²⁺ ions in aqueous solutions. The polymer was electrodeposited on platinum electrode by constant potential electrolysis as PVF⁺ClO₄⁻. Cl⁻ ions were then attached to the polymer matrix by anion exchange and the modified electrode was dipped into Hg²⁺ solution. Hg²⁺ was preconcentrated at the polymer matrix by adsorption and also complexation reaction with Cl⁻. Detection of Hg²⁺ was carried out by differential pulse anodic stripping voltammetry (DPASV) after reduction of Hg²⁺. Mercury ions as low as 5 × 10⁻¹⁰ M could be detected with the prepared electrode and the relative standard deviation was calculated as 6.35% at 1 × 10⁻⁶ M concentration (n = 6). Interferences of Ag⁺, Pb²⁺ and Fe³⁺ ions were also studied at two different concentration ratios with respect to Hg²⁺. The developed electrode was applied to the determination of Hg²⁺ in water samples.     

Silica Meets Tannic Acid: Designing Green Nanoplatforms for Environment Preservation

Hybrid tannic acid-silica-based porous nanoparticles, TA-SiO₂ NPs, have been synthesized under mild conditions in the presence of green and renewable tannic acid biopolymer, a glycoside polymer of gallic acid present in a large part of plants. Tannic acid (TA) was exploited as both a structuring directing agent and green chelating site for heavy metal ions recovery from aqueous solutions. Particles morphologies and porosity were easily tuned by varying the TA initial amount. The sample produced with the largest TA amount showed a specific surface area an order of magnitude larger than silica nanoparticles. The adsorption performance was investigated by using TA-SiO₂ NPs as adsorbents for copper (II) ions from an aqueous solution. The effects of the initial Cu²⁺ ions concentration and the pH values on the adsorption capability were also investigated. The resulting TA-SiO₂ NPs exhibited a different adsorption behaviour towards Cu²⁺, which was demonstrated through different tests. The largest adsorption (i.e., ~50 wt% of the initial Cu²⁺ amount) was obtained with the more porous nanoplatforms bearing a higher final TA content. The TA-nanoplatforms, stable in pH value around neutral conditions, can be easily produced and their use would well comply with a green strategy to reduce wastewater pollution.     

Uptake of Divalent Metal Ions (Cu2+, Zn2+ and Cd2+) by Polysiloxane Immobilized Glycinate Ligand System

ABSTRACT

Porous solid siloxane polymer carrying glycinate functional group of formula –(CH₂)₃NHCH₂COOH has been prepared by the sol-gel process. Treatment of aqueous solutions of divalent metal ions with the polysiloxane glycinate ligand system demonstrates that this material exhibits high potential for preconcentration of metal ions (Cu²⁺, Zn²⁺ and Cd²⁺). The ligand system chemisorbs these divalent metal ions, at optimum conditions, in the order: Cd²⁺ < Zn²⁺ < Cu²⁺. The uptake of copper ions is concentration dependent but it is independent on the presence of other competing ions. Treatment of the glycinate ligand system with acidic solution results in leaching of bound ligands. The highest leaching occurs in presence of copper ions at low pH     

Coumarine–imino–C2-glucosyl conjugate as receptor for Cu in blood serum milieu,on silica gel sheet and in Hep G2 cells and the characterization of the species of recognition

A coumarine–imino–C2-glucosyl conjugate (L) was synthesized and characterized. The conjugate L is found to recognize Cu²⁺ in aqueous HEPES buffer by exhibiting a 95% fluorescence quenching in pH range 7–10 even in the presence of several biologically and ecologically relevant metal ions. Fluorescence on–off behavior has been clearly demonstrated on the basis of the binding variability of Cu²⁺ to L. The binding has been elicited through the changes observed in fluorescence, absorption, ESI-MS and ¹H NMR titrations. All the other thirteen metal ions studied did not show any change in the fluorescence emission. These ions do not interfere with the recognition of Cu²⁺ by L. The structural features of [CuL]₂ complex in both the isomeric forms were established by DFT computational calculations. The utility of L has been demonstrated by showing its sensitivity toward Cu²⁺ on a thin layer of silica gel. The L gives sensitive fluorescence signals for Cu²⁺ even in blood serum and exhibits appropriate fluorescence responses in living cells.     

The state of Cu2+ ions in concentrated aqueous ammonia solutions of copper nitrate

Stabilization of Cu²⁺ ions in concentrated aqueous ammonia solutions of copper nitrate in a wide range of ammonium ion concentrations has been studied by EPR and electronic absorption spectroscopy. Three types of Cu²⁺ associates with different types of orbital ordering have been identified. The ammonium ion concentration in a solution has a decisive effect on the type of orbital ordering of Cu²⁺ ions in associates. In all cases, Cu²⁺ ordering in associates is caused by the existence of bridging OH groups in the axial and equatorial positions of [Cu(NH₃) _n (H₂O)_{6 ? n} ]²⁺ complexes (n < 6). At a high concentration of ammonium ions, weakly bound associates of tetramminecopper with the $d_{x^2 - y^2 }$ ground state are formed. In solutions with low ammonium concentrations, bulky associates with the $d_{y^2 }$ and $d_{x^2 - z^2 }$ ground states and associates of Cu²⁺ ions with the $d_{x^2 - y^2 }$ ground state with hydroxyl groups in the equatorial plane and axial water molecules are formed.     

Fluorescence switch-on sensor for Cu by an amide linked lower rim 1,3-bis(2-picolyl)amine derivative of calix[4]arene in aqueous methanol

A highly selective fluorescence switch on sensor, L for detecting Cu²⁺ has been synthesized by introducing a bis-(2-picolyl)amine moiety at the lower rim of a calix[4]arene platform via amide linkage. Binding properties of L toward ten different biologically relevant Mⁿ⁺ ions have been studied by fluorescence and absorption spectroscopy in methanol and aqueous methanol. L was found to detect Cu²⁺ selectively down to a concentration of 196 and 341 ppb, respectively, in methanol and 1:1 aqueous methanol even in the presence of other metal ions. The composition of the complex has been found to be 1:1 based on the Job plot and is further confirmed by ESI MS. The role of calix[4]arene platform as well as the pre-organized binding core in the selective recognition of Cu²⁺ has been demonstrated by studying appropriate reference molecules. The possible modes of binding of L with Cu²⁺ have been modeled by computational calculations. L and its Cu²⁺ complex could very well be differentiated based on the nano-structural features observed in SEM and AFM.