Electroanalytical Studies of Chromone Based Ionophores for the Selective Determination of Arsenite Ion

Two chemosensors 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐(2‐phenylhydrazone), [I₁] and 4H‐1‐benzopyran‐3‐carboxaldehyde, 4‐oxo‐, 3‐[2‐(2,4‐dinitrophenyl)hydrazone], [I₂] with hydrazone‐NH group as binding site have been shown excellent selectivity for arsenite ion. It is confirmed by the UV‐vis titration that I₂ is more selective than I₁. The performance of the coated graphite electrode (CGE) was found to be better than polymeric membrane electrode (PME) in terms of linear range of 4.89×10^?7–1.0×10^?1 mol L^?1, low detection limit of 8.31×10^?8 mol L^?1 and short response time. The proposed sensors were also used to determine the arsenite ion in different water samples.     

Potentiometric Quantification of the Benzoate Ion in Nonalcoholic Beverages Using a Solid Electrode Modified with a Polypyrrole‐Based Selective Membrane

This work presents the results obtained on the construction of a potentiometric ion‐selective electrode based on a polypyrrole (PPy) selective membrane to quantify the benzoate ion in nonalcoholic beverages. The electrode modification with benzoate (Benz^?1) ion doped‐Ppy was carried out under an imposed potential, while the electrosynthesis optimization was undertaken using the modified Simplex method, such that the film’s sensitivity was maximized toward the benzoate ion. The maximum sensitivity recorded was ?52.02±1.55 mV/decade [Benz^?1] using a graphite powder‐araldite resin composite electrode. During the modified electrode’s characterization it was found out that the response and drift were relatively short, namely 2 min and 0.4 mV min^?1 respectively, within the 7 to 9 pH range, exhibiting a detection limit of 7×10^?4 mol L^?1 and a quantification range of 3×10^?3 at 10^?1 mol L^?1. Selectivity coefficients were evaluated with the Matched Potential Method obtaining in all cases values much less than 1. The benzoate concentration in commercially available juices and sweetened beverages was evaluated comparing the results obtained with the proposed ion‐selective electrode and those of HPLC, the usually accepted technique. A statistical analysis of the results led to the conclusion that there exists no meaningful difference between the results obtained with both techniques, which shows the usefulness of the ion‐selective electrode to proceed with the quantification in real samples.     

A new PVC matrix membrane sensor for determination of praseodymium(III) ion based on bis(salicylaldehyde)thiocarbohydrazone as an ion carrier

The sufficient amounts of bis(salicylaldehyde) thiocarbohydrazone (STCH) as a lipophilic selective element (3%, w/w), sodium nitrobenzene (NB) as a plasticizer (64%, w/w), tetraphenyl borate (NaTPB) as an anionic additive (3%, w/w), and poly vinyl chloride (PVC) as a polymeric matrix (30%, w/w) was employed to form a PVC membrane of a new Pr³⁺ ions selective sensor to apply as an indicator electrode in analytical applications. The best electrode response was observed in the slope (19.5 ± 0.7 mV per decade) over a wide concentrations from lower (1.0 × 10^?6 mol L^–1) to higher (1.0 × 10^?2 mol L^–1) of Pr³⁺ ion solution with a detection limit of 8.5 × 10^–7 mol L^–1. This electrode showed the fast response time about 10 second for praseodymium ion concentration range of 1.0 × 10^–6 to 1.0 × 10^–2 mol L^–1, in the pH range of 2.3–7.9. The matched potential method was applied to study the selectivity of electrode toward Pr³⁺ ions in comparison with many common cations. The results showed the negligible disturbance of all other cations on the proposed praseodymium(III) electrode. The making sensor has been employed successfully as an indicator electrode in the potentiometric titration of praseodymium(III) solution with EDTA at pH 6.0. Moreover the applicability of the sensor was studied in determination of Pr³⁺ ion in mixtures of different ions.     

Self‐Assembled Mercapto‐Compound‐Gold‐Nanoparticle‐Modified Carbon Paste Electrode for Potentiometric Determination of Cadmium(II)

A new modified carbon paste electrode (CPE) based on a recently synthesized ligand [2‐mercapto‐5‐(3‐nitrophenyl)‐1,3,4‐thiadiazole] (MNT), self‐assembled to gold nanoparticles (GNP) as suitable carrier for Cd(II) ion with potentiometric method are described. The proposed electrode exhibits a Nernstian slope of 29.4±1.0 mV per decade for Cd(II) ion over a wide concentration range from 3.1×10^?8 to 3.1×10^?4 mol L^?1. The detection limit of electrode was 2.0×10^?8 mol L^?1 of cadmium ion. The potentiometric responses of electrode based on MNT is independent of the pH of test solution in the pH range 2.0–4.0. It has quick response with response time of about 6 s. The proposed electrode show fairly good selectivity over some alkali, alkaline earth, transition and heavy metal ions. Finally, the proposed electrode was successfully employed to detect Cd(II) ion in hair and water samples.     

Highly Selective Potentiometric Sensor for Determining Phenazopyridine Hydrochloride in Biological Fluids Using N,N′-(Pyromellitoyl)-bis-L-tyrosine Dimethyl Ester

A new membrane selective electrode based on the potentiometric method was developed for the determination of phenazopyridine. The membrane signal is based on the interaction of N,N′-(pyromellitoyl)-bis-L-tyrosine dimethyl ester with phenazopyridine. The sensor displays a linear response with a slope of 61.1 mV decade^?1 for phenazopyridine concentrations in the range of 1.0 × 10^?2–1.0 × 10^?5 mol L^?1 and with detection limit of 8.0 × 10^?6 mol L^?1 of phenazopyridine. The electrode enjoys a fast response time. Application of this potentiometric sensor for phenazopyridine determination in pharmaceuticals, urine, and blood serum samples is reported without any special pretreatment required.     

Voltammetric Ion‐Selective Nanocomposite Carbon Paste Electrode for Determination of Erbium at the Interface Between two Immiscible Electrolyte Solutions

In this study for the first time a novel erbium(III) voltammetric ion‐selective nanocomposite carbon‐paste electrode was introduced based on the concept of ion transfer at the interface between two immiscible electrolyte solutions. N′‐(2‐hydroxy‐1,2‐diphenylethylidene) benzohydrazide (HDB) was used as a selective ionophore in the composition of the carbon paste. The ionophore facilitates transfer of Er(III) from the aqueous solution to the room temperature ionic liquid (RTIL) phase after reduction of the redox probe to maintain charge neutrality. The plot of the peak potential versus the logarithm of the concentration exhibits a Nernstian response (19.9±0.2 mV decade^?1) toward Er(III) in the range of 7.5×10^?7–1.0×10^?1 mol L^?1 with detection limit of 5.0×10^?7 mol L^?1. The proposed sensor shows a fast response time of about 5 s.     

Single‐Piece Solid‐Contact Pb2+‐Selective Electrodes Based on Thiophene Oligomer

A single‐piece solid‐contact Pb²⁺‐selective electrode was prepared by adding a thiophene oligomer into the ion‐selective cocktail directly. The one‐step fabrication yielded an electrode with Nernstian response spanning a wide concentration range of 10^?3–10^?8 mol L^?1, and detection limit as low as 5.6×10^?9 mol L^?1. The electrode had a quick response time of approximately 10–15 s and showed excellent selectivity over the most common univalent and divalent cations. The practical application of the proposed electrode has been tested by determining Pb²⁺ in real water samples.     

Potentiometric Membrane Electrode for Cr(III) Ion Based on a New Aryl Amide Bifunctional Bridging Ligand as a Neutral Carrier

A novel Cr(III) ion‐selective electrode is constructed by incorporating a new aryl amide bifunctional bridging ligand, 2,2′‐bis{[(2″‐benzylaminoformyl)phenxoyl]methyl}‐diethylether (BBPMD) as a neutral carrier into the PVC matrix. The proposed electrode, with optimum membrane composition, exhibits an excellent near‐Nernstian response for Cr³⁺ ion ranging from 2.8 × 10^?6 to 1.0 × 10^?1 mol/L with a detection limit of 8.6 × 10^?7 mol/L and a slope of 19.5 ± 0.2 mV/dec in pH 3.0 nitrate buffer solution at 25 °C. It has an appropriate response time, suitable reproducibility, and good selectivity towards Cr³⁺ ion. The operational pH range of the proposed electrode is 2.5–6.5. The response mechanism was discussed in view of UV‐vis spectroscopy and the A. C. impedance technique. The excellent analytical features of the proposed electrode could lead to its successful application as an indicator electrode in potentiometric titration of Cr³⁺ ion and in the direct determination of Cr³⁺ ion in tea leaves and coffee samples.     

Novel Potentiometric Solid-contact Electrode for the Determination of Fe2+ Ions via MWCNTs-Gemifloxacin Composite

A novel electrode was fabricated for the quantitation of Fe²⁺ ion. It was based on the covalent attachment of the gemifloxacin molecule (the recognition element) to the surface of MWCNTs to be incorporated as an electroactive material. Linear response of Fe²⁺ ions was found in the concentration range of 1×10⁻² mol L⁻¹ to 1×10⁻⁸ mol L⁻¹ with a Nernstian slope of 30.37 ±0.3 (mV/decade) and attained a stable response within 5 s. The sensor exhibited LOD value of 4.8×10⁻⁹ mol L⁻¹. It was applied in the monitoring of Fe²⁺ concentration in multi-vitamins tablets, tap water and milk samples with acceptable recovery ranged from 94.00 % to 102.00 %.     

Application of 1,4-Diaminoanthraquinone as a New Sensing Material for Fabrication of a Iron(III)-Selective Modified Carbon Paste Electrode

In the present work, a novel sensitive electrochemical potentiometric sensor for sensing Fe³⁺ ions based on 1,4-diaminoanthraquinone (DAQ) as a hydrophobic selector element was prepared to implement as an ion selective carbon paste electrode in the aqueous solutions. The adequate amounts of ionophore (5%), paraffin oil (25%) as a binder, Nanosilica (NS: 0.5%) multi-wall carbon nanotubes (MWCNTs: 1%) as a modifier, and graphite powder (68.5%) as an inert matrix was occupied to form the paste. This new FeCP sensor demonstrated a Nernstian slope of 19.7 ± 0.7 mV per decade over widish linear range between 1.0 × 10^–8 to 1.0 × 10^–2 mol L^–1 at working pH range of 1.9–5.0 in the optimized conditions. The average elapsed time to response of electrode was about ~6 s for concentrations from lower (1.0 × 10^?8 mol L^–1) to higher (1.0 × 10^?2 mol L^–1) of Fe³⁺ ion solution. The selectivity of electrode toward Fe³⁺ ions in comparison with other cations was studied by matched potential method. The making FeCP sensor has been put to use successfully as an indicator electrode in analytical applications such as the potentiometric titration and determination of iron(III) ion in blend of different ions.     

Voltammetric Determination of Rutin Using a Carbon Composite Electrode Modified with Copper(II)-Resin

Abstract

The preparation and electrochemical characterization of a carbon composite electrode modified with copper(II)-resin as well as its behavior toward rutin were investigated using cyclic and linear sweep voltammetry. The best voltammetric response was observed for a composite composition of 20% (m/m) copper(II)-resin, 0.10 mol L^?1 KNO₃/10^?6 mol L^?1 HNO₃ solution (pH 6.0) as the supporting electrolyte, and a scan rate of 50 mVs^?1. A linear voltammetric response for rutin was obtained in the concentration range from 9.90 × 10^?7 to 8.07 × 10^?6 mol L^?1, with a detection limit of 2.65 × 10^?8 mol L^?1. The proposed electrode was useful for the quality control and routine analysis of rutin in pharmaceutical formulations.     

Development of an Electrochemical Sensor Based on Covalent Molecular Imprinting for Selective Determination of Bisphenol‐A

In this study, an electrochemical sensor was developed and used for selective determination of bisfenol‐A (BPA) by integrating sol‐gel technique and multi‐walled carbon nanotubes (MWCNTs) modified paste electrode. BPA bounded by covalently to isocyanatopropyl‐triethoxy silane (ICPTS) was synthesized as a new precursor (BPA‐ICPTS) and then BPA‐imprinted polymer (BPA‐IP) sol‐gel was prepared by using tetramethoxysilane (TMOS) and BPA‐ICPTS. Non‐imprinted polymer (NIP) sol‐gel was obtained by using TMOS and (3‐Aminopropyl) triethoxysilane. Both BPA‐IP and NIP sol‐gels were characterized by nitrogen adsorption‐desorption analysis, FTIR, SEM, particle size analyzer and optical microscope. Carbon paste sensor electrode was fabricated by mixing the newly synthesized BPA‐IP with MWCNTs, graphite powder and paraffin oil. The electrochemical characterization of the sensor electrode was achieved with cyclic and differential pulse voltammetric techniques. The response of the developed sensor under the most proper conditions was linear in BPA concentration range from 4.0×10⁻⁹ to 1.0×10⁻⁷ mol L⁻¹ and 5.0×10⁻⁷ to 5.0×10⁻⁵ mol L⁻¹ and the detection limit was 4.4×10⁻⁹ mol L⁻¹. The results unclosed that the proposed sensor displayed high sensitivity and selectivity, superior electrochemical performance and rapid response to BPA.     

Selective Determination of Zn2+ Ion in Various Environmental,Biological and Medicinal Plant Samples Using a Novel Coated Graphite Electrode

Novel Zn²⁺ ion‐selective PVC based coated graphite electrodes were fabricated using the ionophores N‐((1H‐indol‐3‐yl)methylene)thiazol‐2‐amine (I₁), N‐((1H‐indol‐3‐yl)methyl)‐thiazol‐2‐amine (I₂) and 1‐((1H‐indol‐3‐yl)methylene)urea (I₃). Their potentiometric performance was examined in dependence of the addition of plasticizers and anion excluders and compared. It is found that the coated graphite electrode with the composition I₁:KTpClPB:o‐NPOE:PVC=9 : 1.5 : 51 : 38.5 is the best with respect to the wide working concentration range (4.2×10^?8–1.0×10^?1 mol L^?1), low detection limit (1.6×10^?8 mol L^?1) and wide pH range of 3.0–8.0. The proposed electrode was successfully applied to quantify Zn²⁺ in various environmental, biological and medicinal plant samples and used as indicator electrode.     

A Neutral Carrier Membrane Calcium-Sensitive Electrode with Wide Working pH Range

Abstract

A poly(vinyl chloride) (PVC) membrane calcium-sensitive electrode based on a new type of synthetic carrier 1,7-di[2-(1-phenylazo)naphtyl]-1,4,7-trioxaheptan is introduced. This electrode exhibited Nernstian response over the concentration range 1.0×10^?1 - 3.0×10^?8 mol/L Ca²⁺ with a slope of 28.8 mV/pCa in calcium ion buffer solutions. The detection limit for calcium ion was 1.0X10^?8 mol/L. The response time varied from 10 to 30 seconds. The working pH range for the electrode was 3.5 - 12.3 when the concentration of Ca²⁺ was 10^?3 mol/L. The lifetime of the electrode was proved to exceed 8 months. It was applied successfully in the determination of calcium ion in river water, mineral water and cosmetic. A method for the determination of total calcium in urine was developed.     

Chromium(III) Ion Selective Electrode Based on Oxalic Acid Bis(Cyclohexylidene Hydrazide)

A poly(vinyl chloride) membrane sensor based on oxalic acid bis (cyclohexylidene hydrazide) as membrane carrier was prepared and investigated as a Cr(III)‐selective electrode. The electrode reveals a Nernstian behavior (slope 19.8±0.4 mV decade^?1) over a wide Cr(III) ion concentration range 1.0×10^?7–1.0×10^?2 mol dm^?3 with a very low limit of detection (i.e., down to 6.3×10^?8 mol dm^?3). The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 1.7–6.5. The electrode possesses advantage of very fast response, relatively long lifetime and especially good selectivity to wide variety of other cations. The sensor was used as an indicator electrode, in the potentiometric titration of chromium ion and in the determination of Cr(III) in waste water and alloy samples.     

New Validated Potentiometric Determination of Vasodilator Pentoxifylline in its Pharmaceutical Formulations and Biological Fluids

The construction and performance characteristics of pentoxifylline selective electrodes were developed. Two types of electrodes: plastic membrane I and coated wire II were constructed based on the incorporation of pentoxifylline with phosphotungstic acid (PTA). The influence of membrane composition, kind of plasticizer, pH of the test solution, soaking time, and foreign ions on the electrodes was investigated. The electrodes showed a Nernstain response with a mean calibration graph slope of 56.77 ± 0.19 and 55.76 ± 0.71 mV decade^‐1 at 25 °C for electrode I and II respectively, over pentoxifylline concentration range from 1.0 × 10^‐5‐1.0 × 10^‐2 and 9.0 × 10^‐6‐1.0 × 10^‐2 mol L^‐1, with detection limits 4.89 × 10^‐6 and 3.90 × 10^‐6 mol L^‐1 for electrode I and II, respectively. The pH range of the constructed electrodes was 4‐6. Interferences from common cations, alkaloids, sugars, amino acids and drug excipients were reported. The results obtained by the proposed electrodes were also applied successfully to the determination of the drug in its pharmaceutical preparations and biological fluids.     

An All‐solid‐state Polymeric Membrane Ca2+‐selective Electrode Based on Hydrophobic Alkyl‐chain‐functionalized Graphene Oxide

An all‐solid‐state polymeric membrane Ca²⁺‐selective electrode based on hydrophobic octadecylamine‐functionalized graphene oxide has been developed. The hydrophobic composite in the ion‐selective membrane not only acts as a transduction element to improve the potential stability for the all‐solid‐state Ca²⁺‐selective electrode, but also is used to immobilize Ca²⁺ ionophore with lipophilic side chains through hydrophobic interactions. The developed all‐solid‐state Ca²⁺‐selective electrode shows a stable potential response in the linear range of 3.0×10⁻⁷–1.0×10⁻³ M with a slope of 24.7±0.3 mV/dec, and the detection limit is (1.6±0.2 )×10⁻⁷ M (n =3). Additionally, due to the hydrophobicity and electrical conductivity of the composite, the proposed all‐solid‐state ion‐selective electrode exhibits an improved stability with the absence of water layer between the ion‐selective membrane and the underlying glassy carbon electrode. This work provides a simple, efficient and low‐cost methodology for developing stable and robust all‐solid‐state ion‐selective electrode with ionophore immobilization.     

Graphdiyne and Ionic Liquid Composite Modified Gold Electrode for Sensitive Voltammetric Analysis of Rutin

It is significant to develop a point-of-care testing (POCT) method for rapid detection of medicinal molecules. In this paper, a graphdiyne (GDY)-ionic liquid (IL) composite was prepared via one-step facile ultrasound preparation process and then modified on gold (Au) electrode surface by simple casting method. Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of GDY-IL composite. Cyclic voltammetric results proved that GDY-IL composite on the electrode surface could effectively improve electron transfer rate, which meant that GDY-IL composite had high conductivity with big surface area. Finally, the modified electrode exhibited excellent performances for rutin detection with wider linear range (8.0×10⁻⁹ mol L⁻¹–2.0×10⁻⁶ mol L⁻¹ and 2.0×10⁻⁶ mol L⁻¹–1.5×10⁻⁴ mol L⁻¹) and lower detection limit (2.7 nmol L⁻¹, 3S₀/S). The Nafion/GDY-IL/Au electrode showed good sensitivity and high selectivity, which was satisfactory in analytical application to real samples. Therefore, the GDY-IL composite modified electrode has the potential applications in the POCT for electrochemical analysis of various medicinal molecules.     

Voltammetric Determination of 3‐Nitrofluoranthene and 3‐Aminofluoranthene at Boron Doped Diamond Thin‐Film Electrode

The voltammetric behavior of 3‐nitrofluoranthene and 3‐aminofluoranthene was investigated in mixed methanol‐water solutions by differential pulse voltammetry (DPV) at boron doped diamond thin‐film electrode (BDDE). Optimum conditions have been found for determination of 3‐nitrofluoranthene in the concentration range of 2×10^?8–1×10^?6 mol L^?1, and for determination 3‐aminofluorathnene in the concentration range of 2×10^?7–1×10^?5 mol L^?1, respectively. Limits of determination were 3×10^?8 mol L^?1 (3‐nitrofluoranthene) and 2×10^?7 mol L^?1 (3‐aminofluoranthene).     

A Novel Voltammetric Method for the Determination of Maleic Acid Using Silver Amalgam Paste Electrode

An efficient voltammetric method was developed for the determination of maleic acid at a silver amalgam paste electrode (AgA‐PE) in Britton–Robinson buffer pH 2.0. The experimental parameters, such as pH of Britton–Robinson buffer, type of the supporting electrolyte and activation of the electrode surface were optimized. Under the optimal conditions, a linear response was observed over the 2×10^?6–1×10^?4 mol L^?1 maleic acid concentration range, determination limit being 5×10^?7 mol L^?1. A highly stable response, with a relative standard deviation (RSD) of 1.6% for 45 repetitive measurements of 1×10^?4 mol L^?1 maleic acid showed that there was no apparent surface passivation indicating the suitability of the method. The method was successfully applied for direct determination of maleic acid in drinking and river water.