Iodide selective membrane electrodes based on a Molybdenum–Salen as a neutral carrier

A new polymeric membrane electrode (PME) and a coated platinum disk electrode (CPtE) based on Schiff base complex of Mo(VI) as a suitable carrier for I^? ion were described. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. The electrodes exhibited a Nernstian slope of 63.0 ± 0.5 (CPtE) and 60.3 ± 0.4 (PME) mV decade^? 1 in I^? ion over a wide concentration range from 7.9 × 10^? 7 to 1.0 × 10^? 1 M for CPtE and 9.1 × 10^? 6 to 1.0 × 10^? 1 M I^? for PME. The potentiometric response of the electrodes was independent of the pH of the test solution in the pH range 2.0–8.5 with a fast response time (< 10 s). The process of transfer of iodide across the membrane interface was investigated by use of the AC impedance technique. The proposed sensors were successfully applied to direct determination of iodide in samples containing interfering anions, waste water and as indicator electrodes in precipitation titrations.     

Determination of benzalkonium chloride preservative in pharmaceutical formulation of eye and ear drops using new potentiometric sensors

A novel approach for determination of low concentrations of the preservative, benzalkonium chloride (BCCl), in pharmaceutical formulation constitutes is presented. New chemically modified carbon paste electrodes (CMCPEs) are developed. The first is based on an ion-association of BCCl with phosphomolybdic acid (PMA) as the ion-exchanger (BC–PM) dissolved in the mixed plasticizers dibutyl phthalate (DBP) and dioctyl sebacate (DOS) encoded sensor A. In the other electrode, encoded sensor B, the plasticizers DBP and dioctyl phthalate (DOP) are more suitable solvent mediators for the paste. These electrodes exhibit a Nernstian slope of 58.2 ± 0.6 and 62.3 ± 0.7 mV/decade in concentration range 1.3 × 10^? 7–1.7 × 10^? 4 M and 2.5 × 10^? 7–1.7 × 10^? 4 M with the limit of detection of 1.0 × 10^? 7 M and 1.6 × 10^? 7 for sensors A and B, respectively. The sensors have short and stable response time 5–8 s, good reproducibility and can be used in pH range of 5.7–8.6. The present electrodes show good discrimination of BCCl from several inorganic, organic ions and some common drug excipients. These characteristics of the electrodes make them useful in successful determination of BCCl in its pharmaceutical preparations (eye and ear drops) and aqueous solutions. The results obtained were satisfactory with excellent percentage recovery comparable and sometimes better than those obtained by other routine methods for the assay.     

A comparative study on fabrication of Mn2 + selective polymeric membrane electrode and coated graphite electrode

Poly(vinyl chloride)-based membranes of two ligands 2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₁) and N2,N4-di(cyanoethyl)-2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₂) were fabricated and explored as Mn^2 + ion selective electrodes. The performance of the polymeric membranes electrodes of ionophores with different plasticizers (dibutylphthalate, benzoic acid, o-nitrophenyloctyl ether, 1-chloronapthalene and tri-n-butylphosphate) and anion excluders (sodium tetraphenylborate and potassium tetrakis p-(chloro phenyl)borate) was looked in to and the better results were obtained with the membrane having composition L₂: NaTPB: DBP: PVC as 6: 3: 56: 35 (w/w; mg). The coated graphite electrode (CGE) with same composition was also fabricated and investigated as Mn^2 + selective electrode. It was found that CGE showed better response characteristics than PME. The potentiometric response of CGE was independent of pH in the range 3.0–9.0 exhibiting the Nernstian slope 29.5 ± 0.3 mV decade^? 1 of activity and working concentration range 4.1 × 10^? 7–1.0 × 10^? 1 mol L^? 1 with a limit of detection 6.7 × 10^? 8 mol L^? 1. The electrode showed a fast response time of 12 s with a shelf life of 105 days. The proposed CGE could be successfully used for the determination of Mn^2 + ions in different water, soil, vegetables and medicinal plants also used as an indicator electrode in potentiometric titration with EDTA.     

Selective electrodes for [PF6]− and [BF4]− anions based on the associates formed by ionic liquid and cationic dyes

The feasibility of the newly synthesized ionic associates L1 and L2 formed by ionic liquid [C₄mim][PF₆] and cationic dyes (malachite green and methylene blue) has been tested as a novel ionophore for the preparation of anion-selective polymeric membrane electrodes. The electrode exhibits Nernstian response and enhanced potentiometric selectivity towards [PF₆]^? compared to many other anions. The influence of some experimental parameters such as membrane composition, nature of plasticizer and amount of additive on the potential response of the [PF₆]^? sensor are investigated. Under the optimized conditions, the response slopes of the membrane electrodes towards [PF₆]^? are 59.7 ± 0.5 and 58.1 ± 0.5 mV/decade based on ionophore L1 and L2, respectively, in 1.0 × 10^? 5–1.0 × 10^? 1 or 1.0 × 10^? 6–1.0 × 10^? 1 mol/L concentration range. Interestingly, the optimized electrodes based on ionophores L1 and L2 also exhibit Nernstian response characteristics (60.3 ± 0.5 and 56.0 ± 0.5 mV/decade) for tetrafluoroborate anion [BF₄]^? in a wide concentration range. Thus, the proposed sensor has been used for the determination of [PF₆]^? and [BF₄]^? in aqueous ionic liquids samples and the solubility of the [PF₆]^? and [BF₄]^? based ionic liquids in water. The satisfactory results are obtained.     

Bismuth (III) PVC membrane ion selective electrodes based on two compounds: Acylhydrazone and thiosemicarbazone with 1,3,4-thiadiazole

Two Bi^3 + selective electrodes based on L1 and L2 incorporated into a polyvinylchloride (PVC) membrane have been developed. The ionophores L1 and L2 are 2-(5-amino-1,3,4-thiadiazol-2-ylthio)-N′-benzylidene acetohydrazone and 1-(2-(5-amino-1,3,4-thiadiazol-2-ylthio) acetyl)-4-benzoylthiosemicarbazone, respectively. These electrodes are composed of dioctylphtalate (DOP) as a plasticizer and sodium tetraphenylborate (NaTPB) as the lipophilic additive. The best performance was obtained with the membrane compositions of L1 (0.30): PVC (33.22): DOP (66.36): NaTPB (0.12) (%, w/w) and L2 (1.00): PVC (33.00): DOP (65.91): NaTPB (0.09) (%, w/w). Two membrane electrodes show Nernstian response slopes towards Bi^3 + (20.2 and 19.7 mV/decade, respectively) over the concentration range of 10^? 7–10^? 3 and 10^? 7–10^? 2 M, respectively. The effects of the pH and the possible interfering cations were investigated. Both electrodes have a response time of about 10 s, and they can work in a certain concentration aqueous ethanol solution. The prepared electrodes were used as an indicator electrode in potentiometric titration of Bi^3 + ions with EDTA. The membrane sensors were also applied to the determination of Bi^3 + content in compound bismuth aluminate tablets.     

Potentiometric determination of ketoprofen and piroxicam at a new PVC electrode based on ion associates of Rhodamine 6G

The characteristics, performance and application of ion-selective electrodes for ketoprofen and piroxicam ions based on Rhodamine 6G as electrode-active substances are described. These electrodes respond with sensitivities of (58.0 ± 1.0) and (57.0 ± 2.0) mV/decade over the range 1.0 × 10^? 4–1.0 × 10^? 1 and 1.0 × 10^? 4–5.0 × 10^? 2 mol/l at pH 5–9 and 6–10 and a detection limit of 6.3 × 10^? 5 and 3.2 × 10^? 5 mol/l for ketoprofen and piroxicam, respectively. The electrodes are easily constructed at a relatively low cost, have a fast response time and can be used for a period of 5 months without any considerable divergence in potential. The proposed sensor displayed good selectivity for ketoprofen and piroxicam in the presence of several substances and inorganic anions. It was used for the direct assay of ketoprofen and piroxicam in commercial pharmaceutical preparations.     

Polyaniline nanowire electrodes with high capacitance synthesized by a simple approach

Polyaniline (PANI) nanowire electrodes were successfully synthesized by electrodeposition using starch as template. The electrodes were characterized with scanning electron microscope (SEM) and X-ray diffraction technique. SEM images showed that the electrodes electrodeposited using the starch template had nanowire morphology, but the PANI electrodeposited in absent solution had agglomerate block morphology. Cyclic voltammograms at different scan rates and charge–discharge tests were performed in 0.5 M H₂SO₄ aqueous solution. The PANI nanowire electrodes had a high capacitance (882 F g^? 1) and a high stability (5% capacity loss after 500 cycles).     

A comparison of Ga:ZnO and Ga:ZnO/Ag/Ga:ZnO source/drain electrodes for In–Ga–Zn–O thin film transistors

We compared the characteristics of single Ga:ZnO (GZO) and GZO/Ag/GZO multilayer electrodes for source/drain (S/D) contacts in amorphous In–Ga–Zn–O (a-IGZO)-based thin film transistors (TFTs). Due to the existence of a Ag metallic layer between the GZO layers, the GZO/Ag/GZO multilayer electrode exhibited low sheet resistance (3.95 ohm/sq.) and resistivity (3.32 × 10^?5 ohm-cm). The saturation mobility (10.2 cm² V^?1 s^?1) of the a-IGZO TFT with GZO/Ag/GZO S/D electrodes is much higher than that attained for the a-IGZO TFT with single GZO S/D electrodes (0.7 cm² V^?1 s^?1) due to the lower resistivity of the GZO/Ag/GZO multilayer S/D electrode. Furthermore, it is expected that the high transparency of the GZO/Ag/GZO multilayer will allow for the possible realization of fully transparent a-IGZO TFTs.     

Modified carbon paste electrodes for Cu(II) determination

A new Cu²⁺ carbon paste electrode (CPE) using 2,2′-(1E,1′E)-1,1′-(2,2′-azanediylbis (ethane-2,1-diyl)bis(azan-1-yl-1-ylidene))bis(ethan-1-yl-1-ylidene)diphenol (ADEZEDP) has been prepared. The influence of variables including sodium tetraphenylborate (NaTPB), ionophore, and amount of multiwalled carbon nanotubes (MWCNT), CdO nanowires, CdS nanoparticles and palladium nanoparticles loaded on ADEZEDP and Nujol on the electrodes response were studied and optimized. At optimum values of all variables, for each nanomaterial the electrode response was linear in concentration range of 1.0 × 10^? 8 to 1.0 × 10^? 1 mol L^? 1 for ADEZEDP with Nernstian slope. The good performance of electrode viz. Wide applicable pH range (2.0–5.0), fast response time (≈ 6 s), and adequate life time (3 months) indicate the utility of the proposed electrodes for evaluation of Cu²⁺ ion content in various situations. Finally, these electrodes have been successfully applied for the determination of Cu²⁺ ions content in various real samples. The selectivity of proposed electrode was evaluated by separation solution method and fixed interference method.     

Sulphonamide-imprinted sol–gel materials as ionophores in potentiometric transduction

This work proposes different kind of solid-contact graphite-based electrodes for the selective determination of sulphonamides (SPHs) in pharmaceuticals, biological fluids and aquaculture waters. Sulfadiazine (SDZ) and sulfamethoxazole (SMX) were selected for this purpose for being the most representative compounds of this group. The template molecules were imprinted in sol–gel (ISG) and the resulting material was used as detecting element. This was made by employing it as either a sensing layer or an ionophore of PVC-based membranes and subsequent potentiometric transduction, a strategy never reported before. The corresponding non-imprinted sol–gel (NISG) membranes were used as blank. The effect of plasticizer and kind/charge of ionic lipophilic additive was also studied.The best performance in terms of slope, linearity ranges and signal reproducibility and repeatability was achieved by PVC membranes including a high dielectric constant plasticizer and 15 mg of ISG particles. The corresponding average slope was ?51.4 and ?52.4 mV/decade, linear responses were 9.0 × 10^?6 and 1.7 × 10^?5 M, and limits of detection were 0.74 and 1.3 μg/mL for SDZ and for SMX, respectively. Good selectivity with log Kpot < ?0.3 was observed for carbonate, chloride, fluoride, hydrogenocarbonate, nitrate, nitrite, phosphate, cyanide, sulfate, borate, persulphate, citrate, tartrate, salicylate, tetracycline, ciprofloxacin, sulphamerazine, sulphatiazole, dopamine, glucose, galactose, cysteine and creatinine. The best sensors were successfully applied to the analysis of real samples with relative errors ranging from ?6.8 to + 3.7%.     

Immobilization of Bacillus sp. in mesoporous activated carbon for degradation of sulphonated phenolic compound in wastewater

Xenobiotic compounds are used in considerable quantities in leather industries besides natural organic and inorganic compounds. These compounds resist biological degradation and thus they remain in the treated wastewater in the unaltered molecular configurations. Immobilization of organisms in carrier matrices protects them from shock load application and from the toxicity of chemicals in bulk liquid phase. Mesoporous activated carbon (MAC) has been considered in the present study as the carrier matrix for the immobilization of Bacillus sp. isolated from Effluent Treatment Plant (ETP) employed for the treatment of wastewater containing sulphonated phenolic (SP) compounds. Temperature, pH, concentration, particle size and mass of MAC were observed to influence the immobilization behavior of Bacillus sp. The percentage immobilization of Bacillus sp. was the maximum at pH 7.0, temperature 20 °C and at particle size 300 μm. Enthalpy, free energy and entropy of immobilization were ? 46.9 kJ mol^? 1, ? 1.19 kJ mol^? 1 and ? 161.36 J K^? 1 mol^? 1 respectively at pH 7.0, temperature 20 °C and particle size 300 μm. Higher values of ΔH⁰ indicate the firm bonding of the Bacillus sp. in MAC. Degradation of aqueous sulphonated phenolic compound by Bacillus sp. immobilized in MAC followed pseudo first order rate kinetics with rate constant 1.12 × 10^? 2 min^? 1.     

Fabrication of an iron(III) PVC-membrane sensor based on bis-benzilthiocarbohydrazide as a selective sensing material

The construction, performance characteristics, and application of a novel iron(III) membrane sensor based on a new bis-benzilthiocarbohydrazide (BBTC) are reported in this paper. The sensor is prepared by incorporating of BBTC, nitrobenzene (NB), and sodium tetraphenyl borate (NaTPB) into a plasticized poly(vinyl chloride) membrane. The electrode reveals a Nernstian behavior over a wide iron ion concentration range (1.0 × 10^? 2–1.0 × 10^? 7 mol L^? 1), and relatively low detection limit (8.6 × 10^? 8 mol L^? 1). The potentiometric response is independent on the pH of the solution in the range of 1.6–4.3. The electrode shows a very short response time (< 10 s). The proposed electrode can be used for at least nine weeks without any considerable divergence in potentials. It exhibits very good selectivity relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. In fact, the selectivity of the proposed sensor shows great improvements compared to the previously reported electrodes for the iron ion. Also, the sensors accuracy was investigated in two ways: (i) with the potentiometric titration of a Fe(III) solution with EDTA and (ii) with the Fe(III) monitoring in river and wastewater samples.     

Praseodymium analysis in aqueous solution by Pr3+–PVC membrane sensor based on N,N′-bis(4-hydroxysalicylidene)-1-3-phenylenediamine

A new Pr³⁺ poly vinyl chloride PVC membrane sensor based on a membrane containing 3% N,N′-bis(4-hydroxysalicylidene)-1-3-phenylenediamine (HSPDA) as an ionophore, 2% sodium tetraphenyl borate (NaTPB) as an anionic additive, 65% benzyl acetate (BA) as solvent mediator and 30% poly(vinyl chloride) was prepared. This sensor responds to praseodymium ion in a wide linear dynamic range of 1.0 × 10^?6 to 1.0 × 10^?2 mol L^?1 with Nernstian slope of 19.8 ± 0.4 mV per decade and a detection limit of 5.7 × 10^?7 mol L^? 1 in pH range of 3.1 to 9.8. It has a fast response time of ~5 s in the whole concentration range, and can be used for at least 2 months without any considerable divergences in the potentials. The proposed sensor displays an excellent selectivity for Pr³⁺ ions with respect to a large number of alkali, alkaline earth, transition and heavy metal ions. The developed sensor was successfully applied as an indicator electrode in Pr³⁺ ion potentiometric titration with EDTA, and in direct determination of fluoride ion in two mouth wash samples.     

Synthesis of magnetite nanoparticles by surfactant-free electrochemical method in an aqueous system

A simple surfactant-free electrochemical method is proposed for the preparation of magnetite nanoparticles using iron as the anode and plain water as the electrolyte. This study observed the effects of certain parameters on the formation of magnetite nanoparticles and their mechanism in the system, including the role of OH^? ions, the distance between electrodes and current density. We found that OH^? ions play an important role in the formation of magnetite nanoparticles. Particle size can be controlled by adjusting the current density and the distance between electrodes. Particle size increases by increasing the current density and by decreasing the distance between electrodes. Particle formation cannot be favored when the distance between electrodes is larger than a critical value. The magnetite nanoparticles produced by this method are nearly spherical with a mean size ranging from 10 to 30 nm depending on the experimental conditions. They exhibit ferromagnetic properties with a coercivity ranging from 140 to 295 Oe and a saturation magnetization ranging from 60 to 70 emu g^?1, which is lower than that of the corresponding bulk Fe₃O₄ (92 emu g^?1). This simple method appears to be promising as a synthetic route to producing magnetite nanoparticles.     

Preparation and study of a naproxen ion-selective electrode

Naproxen membrane electrodes based on different plasticizers and quaternary ammonium salt tetraoctylammonium (S)-6-methoxy-α-methyl-2-naphthaleneacetate (NAP–TOA) were prepared. The electrode response to naproxen has the sensitivity of ? 59.2 mV decade^? 1 over the linear range of 10^? 4–10^? 1 mol L^? 1 and limit of detection 1.80 × 10^? 5 mol L^? 1. This electrode has a response time 15–20 s and can be used in the pH range 5.5–9.5. The selective coefficients were determined in relation to some organic and inorganic anions and excipients of pharmaceuticals. The notable property and attractive quality of the naproxen electrode are low cost, comfortable application and very long lifetime—about 20 months. The electrode was successfully applied for determination of naproxen in urine samples and pharmaceuticals by the calibration curve method and standard addition method. The obtained results are comparable and sometimes better than those obtained by pharmacopoeial method.     

Biosensor based on laccase immobilized on plasma polymerized allylamine/carbon electrode

In this work, a simple and rapid method was used to functionalize carbon electrode in order to efficiently immobilize laccase for biosensor application. A stable allylamine coating was deposited using a low pressure inductively excited RF tubular plasma reactor under mild plasma conditions (low plasma power (10 W), few minutes) to generate high density amine groups (N/C ratio up to 0.18) on rough carbon surface electrodes. The longer was the allylamine plasma deposition time; the better was the surface coverage. Laccase from Trametes versicolor was physisorbed and covalently bound to these allylamine modified carbon surfaces. The laccase activities and current outputs measured in the presence of 2,2′-azinobis-(3-ethylbenzothiazole-6-sulfonic acid) (ABTS) showed that the best efficiency was obtained for electrode plasma coated during 30 min. They showed also that for all the tested electrodes, the activities and current outputs of the covalently immobilized laccases were twice higher than the physically adsorbed ones. The sensitivity of these biocompatible bioelectrodes was evaluated by measuring their catalytic efficiency for oxygen reduction in the presence of ABTS as non-phenolic redox substrate and 2,6-dimethoxyphenol (DMP) as phenolic one. Sensitivities of around 4.8 μA mg^? 1 L and 2.7 μA mg^? 1 L were attained for ABTS and DMP respectively. An excellent stability of this laccase biosensor was observed for over 6 months.     

Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum

A new sensitive voltammetric sensor for determination of sulfadiazine is described. The developed sensor is based on carbon paste electrode modified with sulfadiazine imprinted polymer (MIP) as a recognition element. For comparison, a non-imprinted polymer (NIP) modified carbon paste electrode was prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods were performed to study the binding event and electrochemical behavior of sulfadiazine at the modified carbon paste electrodes. The determination of sulfadiazine after its extraction onto the electrode surface was carried out by DPV at 0.92 V vs. Ag/AgCl owing to oxidation of sulfadiazine. Under the optimized operational conditions, the peak current obtained at the MIP modified carbon paste electrode was proportional to the sulfadiazine concentration within the range of 2.0 × 10^? 7–1.0 × 10^? 4 mol L^? 1 with a detection limit and sensitivity of 1.4 × 10^? 7 mol L^? 1 and 4.2 × 10⁵ μA L mol^? 1, respectively. The reproducibility of the developed sensor in terms of relative standard deviation was 2.6%. The sensor was successfully applied for determination of sulfadiazine in spiked cow milk and human serum samples with recovery values in the range of 96.7–100.9%.     

Detection of anticancer drug tamoxifen using biosensor based on polyaniline probe modified with horseradish peroxidase

Amperometric biosensor based on horseradish peroxidase immobilized via glutaraldehyde on the polyaniline modified platinum electrode shows evidenced promising characteristics in detecting anticancer drug tamoxifen. The sensor was fabricated simply by adsorbing horseradish peroxidase enzyme on the electrode surface for which Cyclic Voltammetry was used to monitor the electro-catalytic reduction of tamoxifen under diffusion-adsorption controlled conditions. Fourier Transform Infrared Spectroscopy, Cyclic Voltammetry and Electrochemical Impedance Spectroscopic techniques are used to characterize the electrochemical interfacial properties of surface modified electrodes. The first-hand effort on modified biosensor within Platinum/Polyaniline/Horseradish peroxidase biosensor system has demonstrated excellent electro-analytical properties with biosensor sensitivity of 1.6 μA ng mL^? 1. The optimum limit of detection and limit of quantification are 0.07 ng mL^? 1 and 0.29 ng mL^? 1 respectively for the determination of anticancer drug tamoxifen. It is felt that the present study will help in improving our knowledge of cost-effective quantitative determination of tamoxifen in metabolized biological fluids and other pharmaceutical formulations.     

Application of 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea as sensing material for construction of Tm3+-PVC membrane sensor

A thulium(III) membrane sensor was made using 2% sodium tetraphenyl borate (NaTPB), 65% dibutylphthalate (DBP), 30% poly(vinyl chloride) (PVC) and 3% 1-ethyl-3-(2,5-dihydro-4-(3,5-dimethyl-1H-pyrazol-4-yl)-5-oxo-1H-pyrazol-3-yl)thiourea (ET) as an ionophore. Conductometric study shows selectivity of the Et toward Tm³⁺ ions. Nernstian response of 19.6 ± 0.4 mV per decade of thulium concentration was observed, and the electrode worked well in concentration range of 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit (LDL) of 7.2 × 10^? 7 mol L^? 1, in a pH range of 4.3–10.4. The selectivity of the sensor over alkaline, alkaline earth, transition and heavy metal ions was also found to be in a satisfactory range. To check the analytical applicability of the proposed Tm³⁺ sensor, it was successfully used as an indicator electrode in analysis of thulium in certified reference materials.     

Construction of Tm3+-PVC membrane sensor based on 1-(2-thiazolylazo)-2-naphthol as sensing material

In this study, a new thulium(III) membrane sensor was constructed. The proposed membrane sensor was fabricated based on a membrane containing 2% sodium tetraphenyl borate (NaTPB) as an anionic additive, 65% benzyl acetate (BA) as solvent mediator, 3% 1-(2-thiazolylazo)-2-naphthol (TN) as ionophore, and 30% poly(vinyl chloride) (PVC). The proposed Tm³⁺ electrode exhibits a Nernstian response of 19.5 ± 0.2 mV per decade of thulium concentration, and has a lower detection limit of 8.7 × 10^? 7 mol L^? 1. The linear range of the sensors was 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^? 1. It works well in the pH range of 3.2–9.5. Moreover, the recommended selective sensor revealed a comparatively satisfactory selectivity regarding most of the alkali, alkaline earth, some transition and heavy metal ions. The membrane sensor was applied to the determination of fluoride ions in mouth wash samples.