Electrochemical Determination of Copper(II) in Water Samples Using a Novel Ion-Selective Electrode Based on a Graphite Oxide–Imprinted Polymer Composite

A novel copper(II)-selective electrode based on graphite oxide/imprinted polymer composite was developed for the electrochemical monitoring of copper(II) (Cu²⁺) ions. The electrode exhibited highly selective potentiometric response to Cu²⁺ with respect to common alkaline, alkaline earth and heavy metal cations. The composite composition studies indicated that the most suitable composite composition performing the most promising potentiometric properties was 20.0% ionophore (Cu²⁺-ion imprinted polymer), 10.0% paraffin oil, 5.0% multiwalled carbon nanotubes, and 65.0% graphite oxide. The fabricated electrode exhibited a linear response to Cu²⁺ over the concentration range of 1.0?×?10^??6–1.0?×?10^??1?M (correlation coefficient of 0.9998) with a sensitivity of 26.1?±?0.9?mV decade^??1. The detection limit of the fabricated electrode was determined to be 4.0?×?10^??7?M. The electrode worked well in the pH range of 4.0–8.0. The electrode had stable, reversible and fast potentiometric response (3?s). In addition, the electrode had a lifetime of more than 1 year. The analytical applications of the proposed electrode were performed using as an indicator electrode for the potentiometric titration of Cu²⁺ with ethylene diamine tetraacetic acid solution and for the determination of Cu²⁺ of spiked river, dam, and tap water samples. The obtained results for potentiometric titration and water samples were satisfactory.     

Novel Copper(II)‐Selective Membrane Electrode Based on a New Synthesized Schiff Base

A PVC membrane electrode for copper(II) ion based on a recently synthesized Schiff base as a suitable ion carrier was constructed. The electrode exhibits a Nernstian slope of 28.3 ± 0.6 mV per decade of Cu²⁺ over a wide concentration range of 7.0 × 10^?6‐2.6 × 10^?2 M with a detection limit of 5.0 × 10^?6M in the pH range of 4.2–5.8. The response time is about 10s and it can be used for at least 1 month without any considerable divergence in potential. It was successfully applied as an indicator electrode in the potentiometric titration of copper ions.     

New Copper(II) Ion-Selective Membrane Electrode Based on Erythromycin Ethyl Succinate as a Neutral Ionophore

Abstract

The potentiometric response characteristics of a new copper(II) ion-selective PVC membrane electrode based on erythromycin ethyl succinate (EES) as ionophore were investigated. The electrode exhibited a Nernstian response to Cu²⁺ ions over the activity range of 1.5 × 10^?2 to 2.0 × 10^?6 mol L^?1 with a limit of detection of 6.3 × 10^?7 mol L^?1. Stable potentials were obtained in the pH range of 5.5–6.5. The potentiometric selectivity coefficients were calculated by using fixed interference method and revealed no important interferences except for Ag⁺. This electrode was successfully applied as an indicator electrode in determination of copper ions in real water samples.     

Used a new aza-thia-macrocycle as a suitable carrier in potentiometric sensor of copper (II)

A new modified carbon paste electrode for determination of Cu²⁺ made in our laboratory that used a new synthesized macrocycle 7,16-diaza-1-thia-4,10,13,19-tetraoxa-6,17-dioxo-2,3;20,21-dinaphtho-cyclouneicosane as modifier. This sensor exhibits a good affinity toward copper (II) ions over a wide variety of other metal ions. The electrode exhibits a Nernstian slope of 30 (±0.5) mV per decade for copper (II) ions over a wide concentration range (1.0 × 10^?8–1.0 × 10^?2 mol L^?1), with a limit of detection of 7.0 × 10^?9 mol L^?1 (~0.45 ppb). It has a response time of 30 s and can be used for at least 3 months without any considerable divergence in responses. The potentiometric response of the electrode is independent of the pH of test solution in the pH range 3.5–7.5. Finally, it was successfully used as an indicator electrode for determination of copper (II) in real samples such as Karoun river and tap water.     

Highly Selective and Sensitive Membrane Sensors for Copper(II) Ion Based on a New Benzo‐Substituted Macrocyclic Diamide 6,7,8,9,10‐Hexahydro‐2H‐1,13,4,7,10‐benzodioxatriazacyclopentadecine‐3,11(4H,12H)‐dione

Novel PVC membrane (PME) and coated graphite (CGE) Cu²⁺‐selective electrodes based on 5,6,7,8,9,10‐hexahydro‐2H‐1,13,4,7,10‐benzodioxatriazacyclopentadecine‐3,11(4H,12H)‐dione are prepared. The electrodes reveal a Nernstian behavior over wide Cu²⁺ ion concentration ranges (1.0×10^?7–1.0×10^?1 M for PME and 1.0×10^?8–1.0×10^?1 M for CGE) with very low limits of detection (7.8×10^?8 M for PME and 9.1×10^?9 M for CGE). The potentiometric responses are independent of the pH of the test solutions in the pH range 2.7–6.2. The proposed electrodes possess very good selectivities for Cu²⁺ over a wide variety of the cations including alkali, alkaline earth, transitions and heavy metal ions. The practical utility of the proposed electrodes have been demonstrated by their use in the study of interactions between copper ions and human growth hormone (hGH) in biological systems, potentiometric titration of copper with EDTA and determination of copper content of a sheep blood serum sample and some other real samples.     

Highly Sensitive Membrane Electrode Based on a Copper(II)-bis(N-4-Methylphenyl-Salicyldenaminato) Complex for the Determination of Chromate

A highly sensitive polyvinyl chloride (PVC) membrane electrode, based on copper(II)-bis(N-4-methylphenyl-salicyldenaminato) complex, (CuL₂), as a carrier was reported for the determination of chromate ion. The influence of membrane composition, pH, and possible interfering anions on the response of the ion selective electrode was investigated. The sensor exhibited a Nernstian slope of 29.7 mV per decade when the chromate concentration was varied between 2.0 × 10^?7–1.50 × 10^?2 M in a wide pH range (6.0 to 9.0). The detection limit of the ion selective electrode was 9.2 × 10^?8 M. The proposed sensor was used for at least 4 months without any considerable divergence in potential. It was applied as indicator electrode in potentiometric titration of chromate ion with Pb²⁺ and Tl⁺.     

Application of 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo)phenol in construction of ion‐selective PVC membrane electrode for determination of copper (II) in mineral water sample

The potentiometric characteristics of a new Cu²⁺‐selective electrode based on 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo) phenol as an efficient ionophore has been evaluated. The effects of influential parameters on the potentiometric responses such as the amount of plasticizer, the amount of ionophore, pH of the sample solution, and the effect of coexisting ions on the electrode signal were subsequently investigated . The selectivity of the electrode was assessed by calculating the selectivity coefficients using the matched potential method. The optimum ratio of the amount of materials required for the preparation of the electrode was found to be 1.7: 32.1: 64.2: 2.0 corresponding to carboxylated PVC, dimethyl sebacate as solvent mediators, potassium tetrakis (p‐chlorophenyl) borate as the anion localizing agent, and ionophore, respectively. The electrode had a fast response (7s) as well as a satisfactory Nernstian slope (29.26±0.91 mV/decade) to Cu²⁺ over a wide concentration range of 2.0×10^?6‐ 5.0×10^?2 M with a low detection limit of 5.9×10^?7 M. The developed sensor was successfully used for the potentiometric titration of Cu²⁺ ion with EDTA and subsequently, efficient determination of this metal ion in a mineral water sample was performed.     

Determination of 1‐Naphthol with Denatured DNA–Modified Pretreated Glassy Carbon Electrode

Abstract

A highly sensitive electrochemical biosensor for the detection of trace amount of 1‐naphthol was designed. Acid‐denatured DNA were immobilized onto the pretreated glassy carbon electrode (GCE(ox)) surface. Two well‐defined oxidation peaks were observed on the denatured DNA‐modified GCE(ox) at about +0.80 V and +1.10 V (vs. Ag/AgCl) in 0.10‐M acetate buffer (pH 5.0). The peak current of the guanine residue decreased with increasing concentration of 1‐naphthol. The optimum experimental conditions for the detection of 1‐naphthol were explored, and the calibration was linear for 1‐naphthol in the range of 1.0×10^?8?1.1×10^?6 M, with a correlation coefficient of 0.998. The limit of detection (LOD) was 5.0×10^?9 M (S/N=3).     

High Sensitivity and Reproducibility of a Bismuth/Poly(bromocresol purple) Film Modified Glassy Carbon Electrode for Determination of Trace Amount of Cadmium by Differential Pulse Anodic Stripping Voltammetry

This work described a novel type of bismuth/poly(bromocresol purple) film modified glassy carbon electrode (denoted as Bi/Poly(BCP)/GCE) for anodic stripping analysis of trace Cd²⁺. The Bi/Poly(BCP)/GCE was fabricated in situ by depositing simultaneously bismuth and cadmium by reduction at ?1.20 V on the poly(BCP) film using a differential pulse voltammetry. Under the optimum conditions, the anodic stripping peak current response increased linearly with the Cd²⁺ concentrations in a range of 2.0×10^?8–1.0×10^?7 M and 1.0×10^?7–6.0×10^?6 M in 0.1 M NaAc‐HAc buffer solution (pH 5.0) with the detection limit of 6.5×10^?9 M (S/N=3). The Bi/poly(BCP)/GCE performed good reproducibility and high sensitivity. Finally, this proposed method was successfully applied to determine the concentration of Cd²⁺ in water samples.     

A new nano-composite electrode as a copper (II) selective potentiometric sensor

A macrocyclic ligand “7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione” as an efficient ionophore was used into a new Cu²⁺ nano-composite potentiometric carbon paste sensor containing multi-walled carbon nanotubes (MWCNTs), nanosilica particles, and room temperature ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP]Tf₂N). This potentiometric sensor responds to copper ions in a wide linear dynamic range of 4.50 × 10^?8 to 1.00 × 10^?2 mol L^?1 with Nernstian slope of 29.64 ± 0.10 mV per decade. The detection limit of 2.34 × 10^?8 mol L^?1 was obtained at the pH range 3.5–6.0. It has a fast response with response time of about 10 s, and can be used for at least 16 weeks without any considerable divergence in the potentials. The suggested sensor thus allows sensitive, selective, simple, low cost, and stable electrochemical sensing of Cu²⁺ ions in the presence of a large number of alkali, alkaline earth, transition and heavy metal ions. This sensor was successfully applied in the determination of copper ions in water and waste water samples.     

A Novel Modified Carbon Paste Electrode for Potentiometric Determination of Mercury(II) Ion

A new modified carbon paste electrode (CPE) based on a recently synthesized ligand of Ethyl‐2‐(benzoylamino)‐3‐(2‐hydroxy‐4‐methoxyphenyl)‐2‐propenoate (EBHMP) as a suitable carrier for Hg²⁺ ion was described. The electrode exhibit a super Nernstian slope of 48.5±1.0 mV per decade for Hg²⁺ ion over a wide concentration range from 3.0×10^?7–3.1×10^?2 M. The lower detection limits are 1.0×10^?7 M Hg²⁺. The electrode has a fast response time (ca. 5 s), a satisfactory reproducibility and relatively long life time. The proposed sensor shows a fairly good selectivity toward Hg²⁺ ion in comparison to other common cations. The potentiometric responses are independent of the pH of the test solution in the pH range 1.0–4.0. The proposed electrode was used as an indicator electrode in potentiometric titration of mercuric ion with standard solution of EDTA. The direct determination of mercury in spiked wastewater and an amalgam sample gave results that compare favorably with those obtained by the cold vapor atomic absorption spectrometric method.     

Preparation of a solid-state ion-selective electrode based on polypyrrole conducting polymer for magnesium ion

In this study, a potentiometric sensor based on a pencil graphite electrode (PGE) coated with polypyrrole doped with Titan yellow dye (PPy/TY) was prepared for potentiometric determination of magnesium ion in aqueous solutions. The structural characteristics of magnesium sensor electrode (PGE/PPy/TYMg) were studied using scanning electron microscopy and Fourier transform infrared along with energy-dispersive spectroscopy. Under the optimal conditions, the electrode reveals a good Nernstian behavior with slope of 28.27 ± 0.40 mV per decade over the concentration range of 1.0 × 10^?5–5.0 × 10^?2 M and a detection limit of 6.28 × 10^?6 M. The potentiometric response of fabricated electrode toward magnesium ion was found to be independent of the pH of the test solution in the pH range of 4.5–8.0. The electrode showed fast response time (<10 s) and good shelf lifetime (>2 months). The prepared magnesium sensor electrode can also be used as an indicator electrode in potentiometric titration of Mg²⁺ with EDTA with distinguished end point. The electrode revealed good selectivity with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The introduced magnesium electrode was used for measurement of Mg²⁺ ion in real samples without any serious interferences from other ions.     

Electrocatalytic Oxidation and Determination of Dopamine in the Presence of Ascorbic Acid and Uric Acid at a Poly (4‐(2‐Pyridylazo)‐Resorcinol) Modified Glassy Carbon Electrode

A sensitive and selective electrochemical method for the determination of dopamine (DA) was developed using a 4‐(2‐Pyridylazo)‐Resorcinol (PAR) polymer film modified glassy carbon electrode (GCE). The PAR polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of DA in a phosphate buffer solution (PBS) (pH 4.0). The linear range of 5.0×10^?6–3.0×10^?5 M and detection limit of 2.0×10^?7 M were observed. Simultaneous detection of AA, DA and UA has also been demonstrated on the modified electrode. This work provides a simple and easy approach to selective detection of DA in the presence of AA and UA.     

Copper (II) Sensor Based on a Cephaloridine Antibiotic PVC Matrix

ABSTRACT

A poly (vinyl chloride) (PVC) based membrane of cephaloridine as a novel ionophore exhibits good potentiometric response for Cu²⁺ over a wide concentration range (10^?5-10^? M) with a slope of 28.5 mV per decade. The detection limit is 3.5 × 10^?6 M. The response time of the sensor is < 60 s. The electrode has been used for a period of one month and exhibits good selectivity towards Cu²⁺ in comparison to alkali, alkaline earth, transition and heavy metal ions, with no interference caused by Pb²⁺ Cd²⁺ and Fe²⁺ which are known to interfere with many other copper electrodes. The electrode can be used in the pH range from 4.0 to 6.5 and it can also be used in partially non-aqueous medium having up to 10 (v/v) non aqueous content and in the presence of cationic surfactants at concentrations less than 10^?3 M.     

Super-Paramagnetic Nanoparticles by Surface Imprinting on Graphene Oxide Modified Iron (II,III) with Application for the Determination of Ovalbumin by Absorption Spectroscopy

Protein surface imprinting produces materials capable of selective recognition and capture of proteins. Herein, a protein surface imprinted polymer on graphene oxide modified super-paramagnetic Fe₃O₄ nanoparticles is reported. The molecularly imprinted polymer was synthesized by ultrasound-assisted suspension polymerization, using ovalbumin as the template molecule, 3-aminophenylboronie acid as the functional monomer, and methylene-bis-acrylamide as the cross-linking agent. The nanoparticles were approximately 40 nanometers in size and super-paramagnetic. Moreover, these particles demonstrated considerably high adsorption capacity, fast adsorption kinetics, and selective binding affinities toward the template protein ovalbumin. The calibration curve of ovalbumin was linear from 5.0 × 10^?11 to 1.0 × 10^?10 molar. The limit of detection of ovalbumin was 2.0 × 10^?11 M. These results show that this super-paramagnetic material has potential for biological macromolecule separation and determination.     

Antibacterial,DFT and molecular docking studies of metformin complex as active material for the fabrication of copper (II) selective potentiometric sensor

The prepared and characterized metformin ‐copper (II) complex was used as elecroactive material for modification of a new sensitive and selective modified carbon paste electrode (MCPE) for the potentiometric determination of copper (II) in water samples. The performance characteristics of MCPE were carried out. The electrode showed perfect potentiometric response for Cu (II) over concentration range of 1.0 × 10^?6 – 5.0 × 10^?2 mol L^?1 with a detection limit of 1.0 × 10^?6 mol L^?1 with divalent slope value 30.8 ± 0.92 mV decade^?1 over the pH range of 2–6 and exhibits fast response time of 9 s. Also, this electrode exhibited good selectivity towards Cu (II) ions with respect to other metal ions. The obtained results using the proposed electrode were in a good agreement with those obtained using the inductively coupled plasma (ICP) method.     

Magnesium-PVC Membrane Sensor Based on 4,5-Bis(Benzoylthio)-1,3-Dithiole-2-Thione

Abstract

This report describes an attempt to develop potentiometric Mg²⁺ sensors based on a liquid polymeric membrane. Membrane incorporating 4,5-Bis(benzoylthio)-1,3- dithiole-2-thione (Bz₂dmit) as ionophore, with composition Bz₂ dmit:NaTPB:NB:PVC in the ratio 2.5:2.5:65:30 (w/w), exhibits the best result for potentiometric sensing of Mg²⁺ ions. The proposed electrode, based on Bz₂ dmitwith nitrobenzene (NB) as a solvent mediator in a polyvinyl chloride (PVC) membrane matrix, exhibited a near-Nernstian response to Mg²⁺ in the concentration range of 1.0 × 10^?5 to 1.0 × 10^?1 M, with a slope of 29.2 mV per decade of activity of Mg²⁺. The lower limit of detection was 1.0 × 10^?5 M. This sensor showed high selectivity with respect to alkaline, alkaline earth, transition, and heavy metal ions, except for Sr²⁺, and could be used over a pH range of 3.5–9.0. It can be used for at least 2 mo without considerable divergence in potentials and has a relatively fast response of <10 s. It was applied successfully as an indicator electrode in potentiometric titration of Mg²⁺ ions with EDTA.     

PVC-based Cu (II)-Schiff base complex membrane coated graphite electrode for the determination of the triiodide ion

A triiodide-selective electrode based on copper (II)-Schiff base complex as a membrane carrier is proposed. The electrode was prepared by incorporating the carrier into a plasticized polyvinylchloride (PVC) membrane and was directly coated on the surface of a graphite electrode. The obtained electrode showed a near Nernstian slope of 57.0 ± 0.4 mV/decade to I ₃ ⁻ ions over an activity range of 1.0 × 10⁻⁵−1.0 × 10⁻¹ M with a limit of detection of 4.8 × 10⁻⁶ M. The response time of the electrode was fast (5 s) and the electrode could be used for about 2 months without considerable divergence in response. The potentiometric selectivity coefficients were evaluated and displayed anti-Hofmeister behavior. The electrode was used as an indicator electrode in the potentiometric titration of the triiodide ion and in the determination of ascorbic acid in vitamin C tablets. The text was submitted by the authors in English.     

A Biomimetic Potentiometric Sensor Using Molecularly Imprinted Polymer for the Cetirizine Assay in Tablets and Biological Fluids

Despite the increasing number of applications of molecularly imprinted polymers (MIPs) in analytical chemistry, the construction of a biomimetic potentiometric sensor remains still challenging. In this work, a biomimetic potentiometric sensor, based on a non‐covalent imprinted polymer was fabricated for the recognition and determination of cetirizine. The MIP was synthesized by precipitation polymerization, using cetirizine dihydrochloride as a template molecule, methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross linking agent. The sensor showed high selectivity and a sensitive response to the template in aqueous system. The MIP‐modified electrode exhibited Nernstian response (28.0±0.9 mV/decade) in a wide concentration range of 1.0×10^?6 to 1.0×10^?2 M with a lower detection limit of 7.0×10^?7 M. The electrode has response time of ca. 20 s, high performance, high sensitivity, and good long term stability (more than 5 months). The method was satisfactory and used to the cetirizine assay in tablets and biological fluids.     

1,3,4-Trisubstituted-2-azetidinone Derivatives as Novel Receptors for Bismuth(III) Ion-Selective Electrodes: Application in Pharmaceutical and Glass Samples

Abstract

Polymeric membrane electrodes (PMEs) and coated graphite electrodes (CGEs) containing 1,3,4-trisubstituted-2-azetidinone derivatives as ion carriers are reported here for bismuth(III) ion selectivity. These electrodes exhibited Nernstian response for Bi³⁺ ions over a wide concentration range (5.0 × 10^?7 M to 1.0 × 10^?1 M for CGE) with a lower detection limit of 3.98 × 10^?7 M (for CGE) and wide pH range (1.3–5.0). Compared to polymeric membrane electrode, the coated graphite electrode has shown better selectivity for Bi³⁺ ions with respect to common metal ions. Proposed electrodes have been used for the estimation of Bi³⁺ ions in pharmaceutical and glass samples.