Separation of Metal Ions on Titanium(IV) Tungstate Papers

Abstract

Papers impregnated with titanic tungstate have been used to chromatograph 52 cations in 45 aqueous and mixed solvents. Experimentally, a large number of complex cation separations have been achieved easily and rapidly—Au³⁺, Tl³⁺, Ag⁺, Mo⁶⁺, K⁺, Rb⁺, CS⁺, Ni²⁺, Sb²⁺, Bi³⁺, Be²⁺, and Tl⁺ can be easily separated from numerous metal ions. Several quaternary, ternary, and binary separations have also been achieved, and some important separations are discussed.     

Quantitative Separation of Magnesium and Palladium from Numerous Metal Ions on Titanium Tungstate Papers by Electrochromatography

Abstract

Electrochromatography of forty-six metal ions has been performed in fifteen electrolytes on papers impregnated with titanium tungstate by applying different electrical potentials and allowing different time intervals for migration. On the basis of the differential mobility of the cations, which depend on the nature of the complexes formed with the background electrolytes and the ion exchange properties of titanium tungstate, a large number of binary and ternary separations have been achieved. The separations of one metal ion from numerous metal ions have also been accomplished. For example, the following difficult and important separations have been made: Cu²⁺-Cd²⁺-Bi³⁺, Ag⁺-Cu²⁺-Au³⁺, Pd²⁺-Pt⁴⁺-Ir⁴⁺, Hg²⁺-Cd²⁺-Zn²⁺, Ag⁺-Pt⁴⁺, Au³⁺-Pt⁴⁺, Cd²⁺-Bi³⁺ Bi³⁺-Pb²⁺, Bi³⁺-Hg²⁺, Pd²⁺-Ru³⁺, Ga³⁺-In³⁺, La³⁺-Ce⁴⁺, Hg₂ ²⁺-Hg²⁺, Mg²⁺-Al³⁺, Hg²⁺ from forty-five cations, Au3⁺ from forty-one cations, Pd²⁺ from forty-three cations. Magnesium and palladium have been quantitatively separated in 100–200 μg quantities from binary mixtures as well as from synthetic mixtures containing commonly interfering metals.     

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     

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.     

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     

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⁺.     

Regulation of the Peroxidase-Like Activity of nGO,MoS2 and WS2 Nanozymes by Using Metal Cations

Two dimensional nanoparticles (2D-NPs) along with other nanoscale materials have been deemed to be the next generation of artificial enzymes (nanozymes). The low-cost bulk-scale production, ease of storage and modification of such nanomaterials have given nanozymes an advantage over traditional enzymes. Many studies have been aimed at developing methods to increase the performance of these nanozymes, and also identify interfering agents. To investigate the interference of a number of metal cations, we studied the effect of Ti²⁺, Fe²⁺, Ag⁺, Hg²⁺, Co²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Ca²⁺, Zn²⁺ and Mn²⁺ in a nanozyme assays of 2D-NPs using ABTS radical formation. Ti²⁺, Co²⁺, Cu²⁺, Ni²⁺, Ca²⁺, Zn²⁺ and Mn²⁺ ions did not display any notable effect on the peroxidase-like activity of nGO, MoS₂ and WS₂ 2D-NPs. However, Fe²⁺, Ag⁺, Hg²⁺ and Pb²⁺ ions’ effects on the overall ABTS reaction were significant enough to be visualised by partial least square discriminant analysis (PLSDA). We report that, similar to that of many natural enzymes, the nanozyme activity of 2D-NPs is regulated by a number of metal cations allowing their identification and discrimination by using a statistical analysis tool.     

Application of a Novel Hybrid Cation Exchange Material in Metal Ion Separations

A novel hybrid cation exchange material of the class of tetravalent metal acid (TMA) salt, titanium diethylene triamine pentamethylene phosphonate (TiDETPMP) has been synthesized by the sol gel method. The material has been analyzed by spectroscopy and thermal methods. Physico-chemical and ion exchange characteristics have also been studied. The distribution coefficient (K _d ) has been determined in aqueous as well as various electrolyte media/concentrations for Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ (transition metal ions) and Cd²⁺, Hg²⁺, Pb²⁺, Bi³⁺ (heavy metal ions) using TiDETPMP. Based on the differential affinity/selectivity, the breakthrough capacity (BTC) and elution behavior of various metal ions towards TiDETPMP, a few binary and ternary metal ions separations have been carried out.     

Chromogenic sensing of Cu(II) by imino linked thiacalix[4]arene in mixed aqueous environment

Thiacalix[4]arene based imino receptors 4–5 carrying azophenol appendage have been synthesized and studied for their binding abilities towards different metal ions (Li⁺, Na⁺, K⁺, Cd²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺ and Hg²⁺). Receptor 4 showed selective chromogenic sensing for Cu²⁺ ions in mixed aqueous conditions (THF:H₂O, 9:1 v/v).     

Preparation and adsorption selectivity for Hg(II) and Ag(I) of chelating resin immobilizing benzothiazolyl group on crosslinked polystyrene via hydrophilic sulfur‐containing PEG spacer

A new chelating resin incorporating 2‐mercaptobenzothiazole (MBZ) into macroporous chloromethylated polystyrene via hydrophilic spacer of polyethylene glycol containing sulfur was synthesized. The resin was characterized by elementary analysis and infrared spectra. The adsorption capacity of the resin for Ag⁺, Hg²⁺, Cu²⁺, Zn²⁺, and Pb²⁺ as a function of pH was determined. The effects of interference ions, such as Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, on percent recovery were also investigated. The results showed that the resin could effectively remove Hg²⁺ and Ag⁺ from solutions containing a large excess of Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. In column operation, it was observed that Hg²⁺ and Ag⁺ in trace quantities were effectively removed from binary metal ions. The percent recovery of the resin for Hg²⁺ and Ag⁺ was >98.6% and >97.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5034–5038, 2006     

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.     

Synthetic Inorganic Ion-Exchangers. XVI. Thin-Layer Chromatography of Metal Ions on Zirconium Tungstate: Quantitative Separation of Hg(II) from Several Other Metal Ions and from Mixtures

Abstract

Thin-layer chromatography of 23 metal ions in 10 aqueous and mixed solvent systems has been performed on zirconium tungstate ion-exchange material. Several important binary and ternary separations have been achieved. Quantitative separation of Hg(II) from Pb²⁺, Zn²⁺, Cd²⁺, Bi³⁺, Co²⁺, and mixtures has been achieved using 1,4–dioxane as solvent.     

Studies on selective adsorption resins. XXI. Preparation and properties of macroreticular chelating ion exchange resins containing phosphoric acid groups

Macroreticular cation exchange resins containing phosphoric acid groups (RGP) were prepared by the reaction of glycidyl methacrylate–divinylbenzene copolymer [or poly(glycidyl methacrylate)]beads (RG) with phosphoric acid or phosphorous oxychloride, and the adsorption behavior of metal ions on the RGP was investigated. The phosphorylation of the polymer beads could be effectively carried out by treatment of the polymer beads with 85% phosphoric acid at 80°C for 3 h. The RGP obtained from glycidyl methacrylate–divinylbenzene (2 mol %) copolymer beads showed high cation exchange capacity, salt splitting capacity, and adsorption capacity for Cu²⁺, Zn²⁺, Cd²⁺, Ca²⁺, and Ag⁺. On the other hand, the RGP obtained from poly(glycidyl methacrylate)beads had high adsorption capacity for Al³⁺, Fe³⁺, and UO₂²⁺. The RGP prepared by treating the RG with phosphoric acid had a higher selective adsorption for Li⁺ than for Na⁺.     

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.     

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.     

Synthesis,metal ion complexation and antibacterial activities of some thiapodands with lipophilic amide and ester end groups

A series of acyclic analogues of thiacrown ethers (podands) 7–12 with lipophilic amide and ester end groups were synthesized in high yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Podands 7 and 11 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Cd²⁺, Hg²⁺, Zn²⁺ and Pb²⁺ which begins to level off at a mole ratio of 1:1 podand to metal indicating the formation of a stable 1:1 complexes. On the other hand, podand 9 also showed the formation of 1:1 complexes with above metal cations except with Hg²⁺ ion, which formed a 1:2 podand-to-metal ratio complex. An influence of end groups on metal ion selectivity is evident. Podands having ethoxy end groups (podands 8, 10 and 12 exhibit pronounced metal ion selectivity over podands having amino end groups (podands 7, 9 and 11). Compounds 10 and 12 with dithiaethylene units and ethoxy end groups provide the best selectivity for Hg²⁺ and Ag⁺ ions. These results suggest that podands 10 and 12 could be useful for the selective removal of Hg²⁺ and Ag⁺ ions from industrial waste that may contain a variety of toxic heavy and transition metal ions. The in vitro antibacterial activity of the investigated compounds was tested against several microorganisms such as Bacillus subtilis (ATCC 6633), Micrococcus luteus (ATCC 10240), Staphylococcus aureus (ATCC 43300), Escherichia coli (ATCC 25922) and Enterobacter aerogenes (ATCC 13048). The antibacterial activity of podand 10 is significant for M. luteus and B. subtilis compared with other podands under investigation.     

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.     

The Extraction Ability and Sensitivity of Porphyrazine Derivatives Towards Some Transition Metal Cations

The synthesis of novel metal-free and magnesium porphyrazines, peripherally substituted with dithia-dioxa (S₂O₂) and tetrathia (S₄) 14-membered macrocycles were performed by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzo-dioxadithiacyclotetradecine-6,7-dicarbodinitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro 2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbodinitrile (5). The metal-free porphyrazines have been obtained by known route. The structure of compounds were characterized by elemental analysis and ¹H, ¹³C NMR, IR, UV-vis, and MS spectral data. The solvent extraction properties of the synthesized compounds towards some metal cations, such as Ag(I), Hg(II), Cu(II), Mn(II), Cr(III), Ni(II), Pb(II), and Zn(II) have been investigated. The effect of Cu²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Sr²⁺, Al³⁺, Zn²⁺, Ba²⁺, Cd²⁺, Co²⁺, Hg²⁺, and Ag⁺ ions on the absorption spectra of the compounds were investigated by means of spectrophotometric method. Magnesium porphyrazine with S₂O₂ (6) interacted within Hg²⁺ ion specifically of all the tested metal ions.     

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).     

The Separation of the Oxidation States of Some Elements with the Use of Tri-n-butyl Orthophosphate

Abstract

The tri-n-butyl orthophosphate:acetic acid:acetone solvent system has been studied for the paper chromatographic separation of the oxidation states of 16 elements. The separation of As³⁺, As⁵⁺; Cr³⁺, Cr⁵⁺; Fe²⁺, Fe³⁺; Hg⁺, Hg²⁺; Mn²⁺, Mn³⁺, and Mn⁷⁺; Sb³⁺, Sb⁵⁺; Tl⁺, Tl³⁺; Cl^?, ClO₃ ^? Br^? BrO₃ ^?; I^?, IO^? ₃; P₂O^4- ₇ PO^3- ₄, and PO^? ₃ has been achieved. Multiple zones obtained with Fe³⁺ and Tl³⁺ species are discussed.