Facilitated Transfer of Alkali Metal Ions by a Tetraester Derivative of Thiacalix[4]arene at the Liquid–Liquid Interface

The facilitated transfer of alkali metal ions (Na⁺, K⁺, Rb⁺, and Cs⁺) by 25,26,27,28‐tetraethoxycarbonylmethoxy‐thiacalix[4]arene across the water/1,2‐dichloroethane interface was investigated by cyclic voltammetry. The dependence of the half‐wave transfer potential on the metal and ligand concentrations was used to formulate the stoichiometric ratio and to evaluate the association constants of the complexes formed between ionophore and metal ions. While the facilitated transfer of Li⁺ ion was not observed across the water/1,2‐dichloroethane interface, the facilitated transfers were observed by formation of 1 : 1 (metal:ionophore) complex for Na⁺, K⁺, and Rb⁺ ions except for Cs⁺ ion. In the case of Cs⁺ a 1 : 2 (metal:ionophore) complex was obtained from its special electrochemical response to the variation of ligand concentrations in the organic phase. The logarithms of the complex association constants, for facilitated transfer of Na⁺, K⁺, Rb⁺, and Cs⁺, were estimated as 6.52, 7.75, 7.91 (log β₁°), and 8.36 (log β₂°), respectively.     

Facilitated Transfer of Alkali and Alkaline‐Earth Metal Ions by a Calix[4]arene Derivative Across Water/1,2‐Dichloroethane Microinterface: Amperometric Detection of Ca2+

The host–guest complexation reactions between 5,11,17,23‐tetra‐tert‐butyl‐25,27‐diethoxycarbonylmethoxy‐26,28‐dimethoxy calix[4]arene (BDDC4) and alkali and alkaline‐earth metal ions were investigated by facilitated ion transfer processes across water/1,2‐dichloroethane microinterface by using steady‐state cyclic voltammetry and differential pulse voltammetry. The obtained facilitated transfers for Li⁺, Na⁺, K⁺, Rb⁺ and Ca²⁺ were evaluated under the different experimental conditions, at the excess concentrations of metal ions with respect to BDDC4 and vice versa. The association constants having 1 : 1 stoichiometry for Li⁺, Na⁺, K⁺ and Rb⁺ in 1,2‐DCE were determined. Also, we demonstrated that BDDC4 can play an important role for the development of highly selective chemical sensor for Ca²⁺ among alkaline‐metal ions in the concentration range of 0.1–1.0 mM in aqueous solution.     

Studies on the macrocycle mediated transport of some metal cations through a bulk liquid membrane system using kryptofix 22

Competitive transport experiments involving Fe⁺³, Cr⁺³, Ni⁺², Co⁺², Ca⁺², Mg⁺² and K⁺ metal cations from an aqueous source phase through some organic membranes into an aqueous receiving phase have been carried out using 4,13-diaza-18-crown-6 (kryptofix 22) as an ionophore present in the organic membrane phase. Fluxes and selectivities for competitive of the metal cations transport across bulk liquid membranes have been determined. A good selectivity was observed for K⁺ cation by kryptofix 22 in 1,2-dichloroethane (1,2-DCE) membrane system. The sequence of selectivity for potassium ion in the organic solvents was found to be: 1,2-DCE > DCM (dichloromethane) >CHCl₃. The transport of K⁺ cation was also studied in the DCM-1,2-DCE, CHCl₃-1,2-DCE and CHCl₃-DCM binary mixed solvents as membrane phase. A non-linear relationship was observed between the transport rate of K⁺ ion and the composition of these binary mixed solvents. The amount of K⁺ transported follows the trend: DCM-DCE > CHCl₃-DCE > CHCl₃-DCM in the bulk liquid membrane studies. Then, the selective transport of K⁺ cation through a DCM-1,2-DCE bulk liquid membrane was studied by kryptofix 22 as an efficient carrier. The highest transport efficiency was obtained by investigating the influence of different parameters such as the concentration of kryptofix 22 in the membrane phase, pH of the source and the receiving phases and the equilibrium time of the transport process. Maximum transport value of 71.62 ± 1.61% was observed for K⁺ ion after 4 hours, when its concentration was 4 × 10^–3 M.     

Voltammetric determination of facilitated ion transfer across the water/1,2-dichloroethane interface

The facilitated transfer characteristics of Cd²⁺ ion by 4-morpholinoacetophenone-4-ethyl-3-thiosemicarbazone (MAPET) across water/1,2-dicholoroethane (1,2-DCE) interface and its electrochemical properties were investigated by voltammetric measurements. Cyclic voltammetry (CV) was employed to examine the transfer in the conditions of the ligand (organic phase) in excess and the obtained transfer peaks have reversible nature at different metal concentrations and scan rates. The dependence of the obtained half-wave transfer potential on MAPET concentration showed that the equilibrium is effectively displaced towards a 1: 3 (Cd²⁺: ligand) stoichiometry with an association constant of logβ ₃ ⁰ = 12.96 ± 0.09 for the Cd²⁺ ion, corresponding to the TIC/TID mechanism.     

Synthesis and crystal structure of a new N-(2,6-dichlorobenzoyl)-N′,N″-bis(pyrrolidinyl)-phosphoric triamide as a carrier and competitive bulk liquid membrane transport of six metal cations

The competitive metal ion transport experiments of Co⁺², Cd⁺², Ag⁺, Pb⁺², Ni⁺², and Cu⁺² were carried out by N-(2,6-dichlorobenzoyl)-N′,N″-bis(pyrrolidinyl)-phosphoric triamide as a carrier in organic membrane phase. 2,6-Cl₂C₆H₃C(O)NHP(O)[NC₄H₈]₂ has been synthesized and characterized by mass spectrometry IR spectroscopy and single crystal X-ray diffraction. The asymmetric unit of title phosphoric triamide contains one symmetrically independent molecule. The source phase contained equimolar concentrations of metal ions at pH 5 and the receiving phase being buffered at pH 3. The following solvents were examined as membrane: chloroform (CHCl₃), nitrobenzene (NB), 1,2-dichloroethane (1,2-DCE), dichloromethane (DCM), dichloromethane/1,2-dichloroethane (DCM/1,2-DCE). The obtained results show that the selectivity and efficiency of transport for these heavy metal cations change with the nature of the ligand and also the organic solvents, which were used as liquid membrane in these experiments. A good selectivity was observed for Pb⁺² cation by this ligand in all membrane systems. Moreover, the selectivity of metal cations in DCM is higher than other solvents. A non-linear relationship was found between the percent of transport of Pb⁺² cation by this ligand and the compositions of DCM/1,2-DCE and binary solution by this ligand. The effect of several factors such as the nature of carboxylic acids (stearic, fumaric and maleic acid) as surfactant in the membrane phase and the time of transport on transport efficiency of Pb⁺² cation were investigated.     

Facilitated Ion‐Transfer of Sodium Cation by (Anthraquinone‐1‐yloxy) methane‐15‐crown‐5 Across the Water/1,2‐Dichloroethane Microinterface

The transfer of sodium cation facilitated by (anthraquinone‐1‐yloxy) methane‐15‐crown‐5 (L) has been investigated at the water/1,2‐dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone‐1‐yloxy) methane‐15‐crown‐5 obtained was (3.42±0.20)×10^?6 cm² s^?1. The steady‐state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1 : 1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log β_o=11.08±0.03 in the DCE phase. The association constant of other alkali metals (Li⁺, K⁺, Rb⁺) were also obtained.     

Synthesis of novel chromogenic azocalix[4]arenemonoquinones and their binding with alkali metal cations

Five new chromogenic azocalix[4]arenemonoquinones have been synthesized, characterized and examined for their interaction with alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) by UV-visible spectroscopic and cyclic voltammetric techniques. It has been determined that 4a selectively exhibits a significant bathochromic shift in its UV-visible spectrum on interaction with potassium ion in comparison to its treatment with other alkali metal cations. The binding stoichiometry of 4a and potassium ion was established to be 1:1 with an association constant of 3.27 × 10⁴ M^?1. Cyclic voltammetric experiments in 4:1 dichloromethane-acetonitrile also revealed a significant anodic shift (ΔE _(1/1′) = 115 mV) of the original redox waves of 4a on interaction with potassium ion.     

Polymeric membrane coated graphite cesium selective electrode based on 4′,4″(5′) di–tert-butyl di-benzo-18-crown-6

A new PVC membrane coated graphite electrode for cesium ion based on 4′,4″(5′)di–tert-butyl di-benzo-18-crown-6 (DTBDB18C6) as ionophore was prepared. The electrode shows a near Nernstian response of 57.0 ± 1.8 mV decade^?1 over a wide activity range of 6.0 × 10^?6–1.0 × 10^?1 mol L^?1 with a limit of detection 4.0 × 10^?6 mol L^?1. The proposed electrode is suitable for use in aqueous solution in the pH range of 3.0–9.5. It has a fast response time of 10 s and can be used for at least 1 month without any considerable divergence in potential. The selectivity coefficients for Cs⁺ ion with respect to ammonium, alkali, alkaline earth and some selected transition metal ions were determined and showed a superior selectivity over Li⁺, Na⁺ and alkaline earth metal ions. The new electrode was applied for determination of Cs⁺ in spiked tap water. The electrode was also used as indicator electrode in potentiometric titration of Cs⁺ with sodium tetraphenyl borate.     

Trace Analysis of Lead and Copper Ions in Fish Tissue Using Paste Electrodes

Abstract

DNA was immobilized onto a carbon nanotube surface through cyclic voltammetry, in which paste electrode (PE) was subjected to lead and copper trace ion analysis. Optimized conditions for square‐wave stripping voltammetry were then searched. The results indicated three other linear working ranges—3–21 mg l^?1, 2–16 µg l^?1, and 3–17 ng l^?1 Pb(II) Cu(II)—within an accumulation time of 190 s in 0.1‐M ammonium phosphate electrolyte solutions of pH 10.0. At the optimized conditions, the detection limit (S/N) was pegged at 0.4 ng l^?1 (1.93×10^?12 M Pb(II) and 6.29×10^?12 M Cu(II)). And the relative standard deviation at 10 mg l^?1 Pb(II) and Cu(II) was a 0.074 and 0.069% precision, in 15 measurements. The method can be applied to assays of fish tissue.     

Preparation and characterization of nickel hexacyanoferrate films for the removal of cesium ion by electrically switched ion exchange (ESIX)

The method of electrically switched ion exchange (ESIX) involves the sequential application of reduction and oxidation potentials to an ion exchange film to induce the respective loading and unloading of Cs⁺. In this study, four films of nickel hexacyanoferrate were prepared on nickel electrodes with different preparation procedures. Films were characterized by SEM/EDX. Each film shows a different performance with regard to Cs⁺ separation. Scanning electron microscopy was used to characterize the modified film surfaces. Cyclic voltammetry was used to investigate the ion exchange capacity and stability. The four films show a better capacity for Cs⁺ separation compared to previous methods for the deposition of ESIX films. An optimal nickel hexacyanoferrate film was generated when using an applied potential of 0.2 V relative to a saturated calomel electrode (SCE) to generate the nucleation sites, followed by a 1.3 V vs. SCE potential during the growth stage of the film. This film demonstrated the highest film capacity for ion exchange initially (17.3 × 10^?3 C cm^?2) and again after 1000 cycles (11.1 × 10^?3 C cm^?2).     

Oxidation of melatonin on a glassy carbon electrode modified with metallic glucosamines. Synthesis and characterization

In this study, a glassy carbon electrode modified with different cobalt glucosamines (CoGlu-R), iron glucosamines (FeGlu-R), and nickel glucosamines (NiGlu-R) was used for the electroanalytical determination of melatonin in buffer solutions at pH 7.3 using cyclic and square wave voltammetry. The complexes were synthesized and characterized by IR-TF, ¹H-NMR, and UV–visible spectroscopy. When comparing glucosamines of different metals, the influence of the nature of the metal on the activity is not very strong. The most active complex was CoGlu-R. The oxidation peak was used to determine melatonin in the concentration range of 10^?8–10^?5 M with a detection limit of 2.15?×?10^?7 M (LOD). Our results indicate that the current peak is under mass-transport control and probably suggest that chemical reactions coupled with electrochemical steps are involved. The melatonin oxidation current with this kind of modified electrodes is small but this modified electrode shows high selectivity in medium-199 (glutamine, phenol red, glucose, Na⁺, CO₃ ^2?) with human placental tissue; trophoblast and endothelial cells (K⁺, Ca²⁺, traces of Cu²⁺ and Mg²⁺), yet the tryptophan causes interference.     

Study of Bulk Membrane Transport of Some Heavy Metal Cations Using Three Macrocyclic Ligands Containing Oxygen and Nitrogen Heteroatoms

The transport experiments of Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺ and Pb²⁺ metal cations were carried out by dibenzo-18-crown-6 (DB18C6), dibenzyl-diaza-18-crown-6 (Dibenzyl-diaza-18C6) and di-tert-butyl-dibenzo-18-crown-6 (Di-tert-butyl-DB18C6) using chloroform (CHCl₃), 1,2-dichloroethane (1,2-DCE) and nitrobenzene (NB) organic solvents as liquid membranes. The source phase contained equimolar concentration of these metal cations and the source and receiving phases being buffered at pH=5 and pH=3, respectively. The obtained results show that the selectivity and the efficiency of transport for these heavy metal cations change with the nature of the ligand and also the organic solvents, which were used as liquid membranes in these experiments. A good selectivity was observed for silver (I) ion by dibenzyl-diaza-18C6 in all membrane systems. Dibenzo-18C6 and di-tert-butyl-DB18C6 showed the highest transport efficiency for cobalt (II) ion. The effect of stearic acid on transport efficiency was also investigated and the results show that the efficiency of transport of the heavy metal cations increases in the presence of this organic acid.     

Fabrication of a new nanocomposite modified carbon paste Al<Superscript>3+</Superscript>-ion selective electrode based on <Emphasis Type="Italic">N,N</Emphasis>′-dipyridoxyl (1,2-cyclohexanediamine) (PYCA) as an active material

Construction and feature of a nanocomposite modified carbon paste electrode for aluminum(III) ion determination based on N,N′-dipyridoxyl (1,2-cyclohexanediamine) (PYCA) as a novel selector material will be covered by this paper. The optimum composition, Nernstian slope/linear range/detection limit in the forms of calibration graph, response time, utilizable pH range, repeatability and precision of measurements of the aluminum(III) ion using the new fabricated Al³⁺-CPE was evaluated. The optimal composition which performed over Al⁺³ ion concentration range 1.0 × 10^?8 mol L^?1–1.0 × 10^?1 mol L^?1 with near-Nernstian slope equal 20.9 ± 0.2 mV decade^?1 and low detection limit about 5.0 × 10^?9 mol L^?1, was formed of ionophore (PYCA 3 %), binder (paraffin oil 30 %), modifier [multi-wall carbon nanotubes (MWCNTs) 1 %] & [Nanosilica (NS) 0.5 %], and inert matrix (graphite powder 65.5). The request time to give rise Nernstian response of electrode for concentrations from 1.0 × 10^?8 mol L^?1 to 1.0 × 10^?1 mol L^?1 of Al³⁺ ion solution was estimated about ~6 s. The new Al³⁺-CPE was applied in pH range 2.0–5.0 with no consequential change in potential response. To verify the selectivity of electrode toward aluminum(III) ion in the presence of different metallic cations, matched potential method was used. The obtain results in analytical applications reflect the excellent ability of this electrode to play the role as endpoint indicator electrode in both titration and direct potentiometric measurements.     

Study on complexation adsorption behavior of dibenzo-18-crown-6 immobilized on CPVA microspheres for metal ions

Dibenzo-18-crown-6 (DBC) was immobilized on crosslinked polyvinyl alcohol (CPVA) microspheres, resulting in polymer-supported crown ether DBC–CPVA. The complexation adsorption behaviors of DBC–CPVA microspheres towards diverse metal ions were investigated. The experimental results show that among alkali metal ions, the complexation adsorption ability of DBC–CPVA for K⁺ ion is the strongest, and crown ether-metal complex in 1:1 ratio is formed, exhibiting a high adsorption capacity. The adsorption capacities of alkali metal ions on DBC–CPVA are in the order: K⁺ ? Na⁺ > LI⁺ > Rb⁺ > Cs⁺. Among several divalent metal ions, DBC–CPVA exhibits stronger adsorption ability towards Zn²⁺ and Co²⁺ ions, and a “sandwich”-type complex is formed probably in a molar ratio of 2:1 between the immobilized DBC and Zn²⁺ ion as well as between the immobilized DBC and Co²⁺ ion. The adsorption capacities of the several divalent metal ions on DBC–CPVA are in the order: Zn²⁺ > Co²⁺ ? Cd²⁺ > Cu²⁺ > Ni²⁺ > Pb²⁺. The complexation adsorption is exothermic physical physisorption process, and raising temperature leads to the decrease of the adsorption capacity. At the same time, the entropy during the complexation adsorption decreases, so the adsorption process is driven by the decrease of enthalpy.     

Metal-ion recognition-competitive bulk liquid membrane transport of transition and post-transition metal cations using a thioether donor acyclic ionophore

The competitive bulk liquid membrane transport of Cr³⁺, Co²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺ and Pb²⁺ metal cations with a new synthetic sulfur donor acyclic ligand (pseudo-cyclic ionophore), i.e. 1-(2-[(2-hydroxy-3-phenoxypropyl)sulfanyl]ethylsulfanyl)-3-phenoxy-2-propanol; (C₂₀H₂₆O₄S₂), was examined using some organic solvents as membranes. The membrane solvents include: chloroform (CHCl₃), 1,2-dichloroethane (1,2-DCE), dichloromethane (DCM), nitrobenzene (NB), chloroform-nitrobenzene (CHCl₃-NB) and chloroform-dichloromethane (CHCl₃-DCM) binary mixtures. The transport process was driven by a back flux of protons, maintained by the buffering the source and receiving phases with pH 5 and 3, respectively. The aqueous source phase consisted of a buffer solution (CH₃COOH/CH₃COONa) at pH = 5 and containing an equimolar mixture of these seven metal cations. The organic phase contained the acyclic ligand, as an ionophore and the receiving phase consisted of a buffer solution (HCOOH/HCOONa) at pH = 3. For these systems that displayed transport behaviour, sole selectivity for Ag⁺ cation was observed under the employed experimental conditions in this investigation. The amount of Ag⁺ transported follows the trend: 1,2-DCE > CHCl₃ > DCM > NB in the bulk liquid membrane studies. The transport of the metal cations in CHCl₃-NB and CHCl₃-DCM binary solvents is sensitive to the solvent composition. The influence of the stearic acid, palmitic acid and oleic acid in the membrane phase on the ion transport was also investigated.     

Preparation of Cu (II) imprinted polymer electrode and its application for potentiometric and voltammetric determination of Cu (II)

The Cu (II) imprinted polymer glassy carbon electrode (GCE/Cu-IP) was prepared by electropolymerization of pyrrole at GCE in the presence of methyl red as a dopant and then imprinting by Cu²⁺ ions. This electrode was applied for potentiometric and voltammetric detection of Cu²⁺ ion. The potentiometric response of the electrode was linear within the Cu²⁺ concentration range of 3.9 × 10^?6 to 5.0 × 10^?2 M with a near-Nernstian slope of 29.0 mV decade^?1 and a detection limit of 5.0 × 10^?7 M. The electrode was also used for preconcentration anodic stripping voltammetry and results exhibited that peak currents for the incorporated copper species were dependent on the metal ion concentration in the range of 1.0 × 10^?8 to 1.0 × 10^?3 M and detection limit was 6.5 × 10^?9 M. Also the selectivity of the prepared electrode was investigated. The imprinted polymer electrode was used for the successful assay of copper in two standard reference material samples.     

Solid-phase extraction of Pb2+ ion from environmental samples onto L-AC-Ag-NP by flame atomic absorption spectrometry (FAAS)

The development of a solid-phase extraction (SPE) procedure for the pre-concentration of trace amounts of Pb²⁺ ion on 2-furan-2-yl-1-furan-2-ylmethyl-1H-benzoimidazole loaded on activated carbon modified with silver nanoparticles (L-AC-Ag-NP) was presented. The metal ion retained on the sorbent was quantitatively determined via complexation with the ligand. The complexed metal ion was efficiently eluted using 10 mL of 4 mol L^?1 sulphuric acid in 10 w/v% acetone. The influences of the analytical parameters, including pH, amounts of the ligand and the solid phase, eluent conditions and sample volume, on the recoveries of the metal ion were optimised. Using the optimised parameters, the linear response of the SPE method for Pb²⁺ ion were in the ranges of 0.2–160 µg L^?1, and the detection limit for Pb²⁺ ion was 0.034 µg L^?1. The proposed method exhibits a pre-concentration factor (PF) of 80 and an enhancement factor of 30 for Pb²⁺ ion. The presented results demonstrate the successful application of the proposed method for the determination of Pb²⁺ ion in some real samples with high recoveries (>93%) and reasonable relative standard deviation (RSD < 2%).     

Cu(II) Hexacyanoferrate(III) Modified Carbon Paste Electrode; Application for Electrocatalytic Detection of Nitrite

Copper hexacyanoferrate (CuHCF) film‐modified carbon paste electrode (CPE) has been prepared from various electrolytic aqueous solutions using consecutive cyclic voltammetry. The cyclic voltammograms showed the direct deposition of CuHCF films from the mixing of Cu²⁺ and Fe(CN)₆^3? ions and each time with one of the six cations: H⁺, Na⁺, K⁺, NH₄⁺, Mg²⁺, and Al³⁺. The CuHCF film showed a single redox couple that exhibited a cation effect (Na⁺, K⁺, Mg²⁺, and NH₄⁺) and anion effect (Cl^?, NO₃^?, SO₄^2?, ClO₄^?, and BrO₃^?) in the cyclic voltammograms. Voltammetric studies have indicated that in presence of nitrite, the cathodic peak current of CuHCF increases, followed by a decrease in the corresponding anodic current. This indicated that nitrite was reduced by the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. The process of reduction and its kinetics were investigated by using cyclic voltammetry, differential pulse voltammetry, chronoamperometry and chronocoulometry techniques. The electrocatalytic ability about 800 mV can be seen. The rate constant of the catalytic reduction of nitrite was found to be 7.9×10⁵ cm³ mol^?1 s^?1. Linearity range obtained was 5×10^?5?8.4×10^?3 by cyclic voltammetry and 8×10^?6?1.3×10^?3 and 4×10^?3?2×10^?2 by differential pulse voltammetry.     

Simultaneous voltammetric analysis of lead,copper and mercury ions by carbon paste electrode based on 1-(3-aminopropyl) imidazole modified polymer

In this study, a carbon paste electrode modified with a novel 1-(3-aminopropyl) imidazole functionalised crosslinked chlorosulfonated poly(styrene)-divinyl benzene polymer was used for selective and sensitive determination of the trace amounts of Pb²⁺, Cu²⁺ and Hg²⁺ ions by square wave anodic stripping voltammetry. The effect of some parameters such as paste composition, pH, preconcentration time, reduction potential and time, type of supporting electrolyte and potential scan rate on the determination of metal ions were investigated to find the optimal conditions. The effective open-circuit accumulation of the studied metal ions was succeeded only by the modification of the carbon paste electrode with functional polymer. For 6 min open-circuit preconcentration, the detection limit of Pb²⁺, Cu²⁺ and Hg²⁺ was found to be 5, 9 and 14 µgL^?1, respectively at 100 mVs^?1. The results confirmed that the lower concentration levels of these trace metal ions can be determined with the increase of preconcentration time and/or potential scan rate. Good detection limits and large dynamic concentration ranges were also obtained for their binary and ternary mixtures. The optimised method was successively applied to determine the concentration of Pb²⁺, Cu²⁺ ions in the tap water sample and Cu²⁺ ion in the waste water sample in the presence of possible interfering species (RSD<1%, recoveries 96–110% for 4 min preconcentration).