Fluoride determination in some mouth wash preparations by a novel La(III) graphite coated membrane sensor based on amitraz

Solution studies on the binding properties of N-2,4-dimethylphenyl-N′-ethylformamidine (amitraz) toward nine lanthanide ions including lanthanum, cerium, neodium, samarium, europium, gadolinium, terbium, dysprosium, ytterbium and some other transition and heavy metal ions such as copper, lead, cobalt, nickel ions, showed a selective 1:1 complexation between amitraz and lanthanum ions. Consequently, amitraz was applied as an ion carrier in construction of a novel poly(vinyl chloride) membrane sensor for La(III). The sensor has a linear dynamic range of 1.0 × 10⁻¹ to 1.0 × 10⁻⁷ M with a Nernstian slope of 19.8 ± 0.2 mV per decade and a detection limit of 8.0 × 10⁻⁸ M. The proposed sensor displays a fast response time (<8 s), and can be used for at least 2 months without any considerable divergences in the potentials. The La(III) membrane sensor revealed comparatively good selectivity with respect to most of cations including alkaline, alkaline earth, and some transition and heavy metal ions. It could be used in a pH range of 3.0-9.0. The proposed membrane electrode was used as an indicator electrode in the potentiometric titration of La(III) ions with an EDTA solution, and also in the determination of fluoride concentration in some mouth wash preparations.     

PVC-based dicyclohexano-18-crown-6 sensor for La(III) ions

A new ion-selective electrode (ISE) based on dicyclohexano-18-crown-6 (DC18C6) as a neutral carrier is developed for lanthanum(III) ions. The electrode comprises of dicyclohexano-18-crown-6 (6%), PVC (33%), and ortho-nitrophenyl octyl ether (o-NPOE) (61%). The electrode shows a linear dynamic response in the concentration range of 10⁻⁶ to 10⁻¹ M with a Nernstian slope of 19 mV per decade and a detection limit as 5×10⁻⁷ M. It has a response time of <30 s and can be used for at least 5 months without any significant divergence in potentials. The selectivity coefficients for mono-, di-, and trivalent cations indicate good selectivity for La(III) ions over a large number of interfering cations. The sensor has been used as an indicator electrode in the potentiometric titrations of La(III) with EDTA. The membrane is successfully applied in partially non-aqueous medium. It can be used in the pH range 4-9.     

Development of a Cr(III)-specific potentiometric sensor using Aurin tricarboxylic acid modified silica

A new chelating resin, Aurin tricarboxylic acid modified silica, was synthesized. The resin behaves as a selective chelating ion exchanger for Cr(III) at a pH 3.8-5.5. A polyvinyl chloride-based membrane electrode of the modified silica has been fabricated and explored as sensor for Cr(III) ions. The membrane works well over the concentration range 7.0 × 10⁻⁶ to 1 × 10⁻¹ M of Cr(III) with a Nernstian slope of 19.0 mV per decade of concentration. The response time of the sensor is 10 s and it can be used for a period of 5 months. The performance of the sensor is best in the pH range 3.5-6.5 and it also works well in partially non-aqueous medium. The selectivity coefficient values depicts that the membrane exhibits good selectivity over a number of interfering ions. Moreover, the membrane sensor has been applied to analyse the concentration of chromium in certified steel sample and food materials with greater than 97% accuracy.     

A selective and sensitive carbon composite coated platinum electrode for aluminium determination in pharmaceutical and mineral water samples

A novel coated wire electrode (CWE) for Al(III) ions is described based on 2-(1H-benzo[d]imidazole-1-yl)-1-phenylethanoneoxime as a new ionophore in carbon-PVC composite. The sensor exhibits significantly enhanced selectivity toward Al³⁺ ions over the concentration range 4.3 × 10⁻⁷ to 5.0 × 10⁻² M with a lower detection limit of 2.5 × 10⁻⁷ M and a Nernstian slope of 19.41 ± 0.52 mV decade⁻¹ of aluminium activity. This sensor has a short response time of about 10 s and is reproducible and stable for at least forty-five days. This proposed CWE which is designed for the first time revealed good selectivity for Al(III) over a wide variety of other cations. The performance of the sensor is best in the pH range of 3.1-5.5 and it also works well in partially non-aqueous medium. Moreover, the assembly has been successfully used as an indicator electrode in the potentiometric titration of aluminium (III) against EDTA and also in determining Al(III) quantitatively in pharmaceutical and mineral water samples.     

Ion imprinted polymer based ion-selective electrode for the trace determination of dysprosium(III) ions

Ion-selective electrode (ISE) was designed by dispersing the dysprosium(III) IIP particles in 2-nitrophenyloctyl ether plasticizer and then embedded in polyvinyl chloride matrix. The ISE shows a Nernstian response for dysprosium(III) over a wide concentration range (8.0 × 10⁻⁶ to 1.0 × 10⁻¹ M) with a slope of 21.7 mV per decade. The limit of detection was 2 × 10⁻⁶ M. This sensor has a very fast response time (∼10 s) and offers high selectivity compared to conventional chemical sensors towards dysprosium(III) with respect to several alkali, alkaline earth and transition metal ions as the selectivity is 10-100-fold better. The sensor was used for determination of dysprosium(III) ions by potentiometric (EDTA) titration and has been successfully demonstrated for the determination of fluoride in mouth wash solution.     

Novel coated-graphite membrane sensor based on N,N′-dimethylcyanodiaza-18-crown-6 for the determination of ultra-trace amounts of lead

A novel selective membrane electrode for determination of ultra-trace amount of lead was prepared. The PVC membrane containing N,N′-dimethylcyanodiaza-18-cown-6 (DMCDA18C6) directly coated on a graphite electrode, exhibits a Nernstian response for Pb²⁺ ions over a very wide concentration range (from 1.0×10⁻² to 1.0×10⁻⁷ M) with a limit of detection of 7.0×10⁻⁸ M (∼14.5 ppb). It has a fast response time of ∼10 s and can be used for at least 2 months without any major deviation in potential. The electrode revealed very good selectivity with respect to all common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as an indicator electrode in potentiometric titration of lead ions and in determination of lead in edible oil, human hair and water samples. The proposed sensor was found to be superior to the best Pb²⁺-selective electrodes reported in terms of detection limit and selectivity coefficient.     

Highly selective and sensitive thiocyanate membrane electrode based on nickel(II)-1,4,8,11,15,18,22,25-octabutoxyphthalocyanine

A highly selective membrane electrode based on nickel(II)-1,4,8,11,15,18,22,25-octabutoxyphthalocyanine (NOBP) is presented. The proposed electrode shows very good selectivity for thiocyanate ions over a wide variety of common inorganic and organic anions. The sensor displays a near Nernstian slope of −58.7 ± 0.6 mV per decade. The working concentration range of the electrode is 1.0 × 10⁻⁶ to −1.0 × 10⁻¹ M with a detection limit of 5.7 × 10⁻⁷ M (33.06 ng/mL). The response time of the sensor in whole concentration ranges is very short (<10 s). The response of the sensor is independent on the pH range of 4.3-9.8. The best performance was obtained with a membrane composition of 30% PVC, 65% dibutyl phthalate, 3% NOBP and 2% hexadecyltrimethylammonium bromide. It was successfully applied to direct determination of thiocyanate in biological samples, and as an indicator electrode for titration of thiocyanate ions with AgNO₃ solution.     

Lead ion-selective electrodes based on polyphenylenediamine as unique solid ionophores

A novel membrane electrode for Pb(II) ion detection based on semi-conducting poly(m-phenylenediamine) microparticles as a unique solid ionophore was fabricated. The electrode exhibited significantly enhanced response towards Pb(II) over the concentration range from 3.16 × 10⁻⁶ to 0.0316 M at pH 3.0-5.0 with a low detection limit of 6.31 × 10⁻⁷ M, a high sensitivity displaying a near-Nernstian slope of 29.8 mV decade⁻¹ for Pb(II). The electrode showed a long lifetime of 5 months and a short response time of 14 s. A systematical investigation on the effect of anion excluder and various foreign ions on the selectivity of the electrode by a fixed interference method suggests that all other metal ions hardly ever interfere with the determination of Pb(II) except high concentration Hg(II). The electrode was successfully used as an indicator electrode in the potentiometric titration of Pb(II) with EDTA. Furthermore, the electrode has been used to satisfactorily analyze four types of real-world samples like spiked human urine, spiked tap water, and river water containing interfering ions like Na(I), Ca(II), Mg(II), Zn(II), Pd(II), Fe(III), K(I), Cu(II) and Hg(II) up to 8.04 × 10⁻⁴ M, demonstrating fast response, high selectivity, good recovery (96.6-121.4%), good repeatability (RSD 0.31-6.45%), and small relative error (5.0%).     

A cerium(III) selective polyvinyl chloride membrane sensor based on a Schiff base complex of N,N'-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine

A polyvinyl chloride (PVC) based membrane sensor for cerium ions was prepared by employing N,N′-bis[2-(salicylideneamino)ethyl]ethane-1,2-diamine as an ionophore, oleic acid (OA) as anion excluder and o-nitrophenyloctyl ether (o-NPOE) as plasticizer. The plasticized membrane sensor exhibits a Nernstian response for Ce(III) ions over a wide concentration range (1.41 × 10⁻⁷ to 1.0 × 10⁻² M) with a limit of detection as low as 8.91 × 10⁻⁸ M. It has a fast response time (<10 s) and can be used for 4 months. The sensor revealed a very good selectivity with respect to common alkali, alkaline earth and heavy metal ions. The response of the proposed sensor is independent of pH between 3.0 and 8.0. It was used as an indicator electrode in potentiometric titration of fluoride, carbonate and oxalate anions and determination of cerium in simulated mixtures.     

The first use of a Rh(III) complex as a novel ionophore for thiocyanate-selective polymeric membrane electrodes

The feasibility of a newly synthesized Rh(III) complex, Rh[(trpy)(bpy)Cl](PF₆)₂, as a novel ionophore for the preparation of anion-selective polymeric membrane electrodes was tested. The ionophore exhibited anti-Hofmeister behavior with enhanced potentiometric selectivity toward thiocyanate ion compared to other anions. The influence of some experimental parameters such as membrane composition, nature and amount of plasticizer and additive and concentration of internal solution on the potential response of the SCN⁻ sensor were investigated. The electrode exhibits a Nernstian response for SCN⁻ over a wide concentration range (1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M) with a slope −58.7 ± 0.5 mV per decade and a detection limit of 4.0 × 10⁻⁶ M (0.23 ppm). It could be used in a pH range of 3.0-8.0 and has a fast response time of about 15 s. The proposed sensor was used for the determination of thiocyanate ions in real samples such as urine and saliva of smokers and nonsmokers and, as an indicator electrode, in potentiometric titrations of SCN⁻ ion.     

Voltammetric performance and application of a sensor for sodium ions constructed with layered birnessite-type manganese oxide

The preparation and electrochemical characterization of a carbon paste electrode modified with layered birnessite-type manganese oxide for use as a sodium sensor is described. The effects of powder synthesis process (sol-gel and redox precipitation) for birnessite on the electrochemical activity of the sensor was investigated by cyclic voltammetry. The carbon paste electrode modified with birnessite-type manganese oxide that was synthesized by the sol-gel method showed a best electrochemical for sodium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and consequently the sodium ions extraction into the birnessite structure. The best voltammetric response was obtained for an electrode composition of 15% (w/w) birnessite oxide in the paste, a TRIS buffer solution of pH 8.0 and a scan rate of 50 mV s⁻¹. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 7.89 × 10⁻⁵ to 3.49 × 10⁻⁴ mol L⁻¹ with a slope of 37.5 μA L mmol⁻¹ and a detection limit (3σ/slope) of 3.43 × 10⁻⁵ mol L⁻¹ using cyclic voltammetry. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples.     

Zirconium ion selective electrode based on bis(diphenylphosphino) ferrocene incorporated in a poly(vinyl chloride) matrix

A novel potentiometric zirconium - PVC matrix membrane sensor incorporating bis(diphenylphosphino) ferrocene as an electroactive material and tris(2-ethylhexyl)phosphate as solvent mediator is described. In mixed acetate buffer solution of pH 4.8, the sensor displays a rapid and linear response for zirconium ion over the concentration range 1.0 × 10⁻¹ to 1.0 × 10⁻⁷ mol L⁻¹ with a good slope of 59.7 ± 0.3 mV per decade and detection limit 1.8 × 10⁻⁸ mol L⁻¹. The best performance was obtained with membrane composition 33% PVC, 65% TEHP, 1% NaTPB and 1% ionophore. The proposed electrode revealed excellent selectivity for zirconium ion over a wide variety of alkali, alkaline earth, transition and heavy metal ions and could be used in a pH range of 4.15-7.8. The electrode was applied for at least 1 month without any considerable divergence in the potential responses. The practical utility of the electrode has been demonstrated by its use as an indicator electrode in the potentiometric titration of zirconium ions with sodium fluoride and in determination of zirconium ion in some alloy, tape and waste water samples.     

Highly selective and sensitive copper membrane electrode based on a new synthesized Schiff base

Bis(2-hydroxyacetophenone)butane-2,3-dihydrazone (BHAB) was used as new N-N Schiffs base which plays the role of an excellent ion carrier in the construction of a Cu(II) membrane sensor. The best performance was obtained with a membrane composition of 30% poly(vinyl chloride), 55% o-nitrophenyloctyl ether (NPOE), 7% BHAB and 8% oleic acid (OA). This sensor shows very good selectivity and sensitivity towards copper ion over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. The effect of membrane composition and pH and influence of additive anionic on the response properties of electrode were investigated. The electrode exhibits a Nernstian behavior (with slope of 29.6 mV per decade) over a very wide concentration range (5.0 × 10⁻⁸ to 1.0 × 10⁻² mol L⁻¹) with a detection limit of 3.0 × 10⁻⁸ mol L⁻¹ (2.56 ng mL⁻¹). It shows relatively fast response time, in whole concentration range (<15 s), and can be used for at least 12 weeks in the pH range of 2.8-5.8. The proposed sensor was successfully used to determination of copper in different water samples and as indicator electrode in potentiometric titration of copper ion with EDTA.     

Construction of a novel molecularly imprinted sensor for the determination of O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrophenyl)methinephosphonate

A novel voltammetric sensor for O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrophenyl)methinephosphonate (Phi-NO₂) based on molecularly imprinted polymer (MIP) film electrode is constructed by using sol-gel technology. The sensor responds linearly to Phi-NO₂ over the concentration range of 2.0 × 10⁻⁵ to 1.0 × 10⁻⁸ mol L⁻¹ and the detection limit is 1.0 × 10⁻⁹ mol L⁻¹ (S/N = 3). This sensor provides an efficient way for eliminating interferences from coexisting substances in the solution. The high sensitivity, selectivity and stability of the sensor demonstrates its practical application for a simple and rapid determination of Phi-NO₂ in cabbage samples.     

p-Aminobenzoate ion determination in pharmaceutical formulations by using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely, Pt|Hg|Hg₂(PABzt)₂| graphite, where PABzt stands for p-aminobenzoate ion, are described. This electrode responds to PABzt with sensivity of (58.1±1.0) mV per decade over the range 1.0×10⁻⁴ to 1.0×10⁻¹ mol l⁻¹ at pH 6.5-8.0 and a detection limit of 3.2×10⁻⁵ mol l⁻¹. The electrode shows easy construction, fast response time (within 10-30 s), low-cost, and excellent response stability (lifetime greater than 6 months, in continuous use). The proposed sensor displayed good selectivity for p-aminobenzoate in the presence of several substances, especially, concerning carboxylate and inorganic anions. It was used to determine p-aminobenzoate in pharmaceutical formulations by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by an HPLC procedure.     

Sub-micro level monitoring of beryllium ions with a novel beryllium sensor based on 2,6-diphenyl-4-benzo-9-crown-3-pyridine

The 2,6-diphenyl-4-benzo-9-crown-3-pyridine (DPCP) was used as an excellent ionophore in construction of a coated graphite poly(vinyl chloride) (PVC)-based membrane sensor. The best performance was obtained with a membrane composition of 30% poly(vinyl chloride), 60% o-nitrophenyloctyl ether (NPOE), 5% 2,6-diphenyl-4-benzo-9-crown-3-pyridine and 5% sodium tetraphenyl borate (TBP). This sensor shows very good selectivity and sensitivity towards beryllium ion over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. The sensor revealed a great enhancement in selectivity coefficients and sensitivity for beryllium, in comparison with the previously reported beryllium electrodes. The electrode exhibits a Nernstian behavior (with slope of 29.6 mV per decade) over a very wide concentration range (1.0×10⁻⁷ to 1.0×10⁻¹) with a detection limit of 4.0×10⁻⁸ M (360 pg ml⁻¹). It shows relatively fast response time, in whole concentration range (<10 s), and can be used for at least 12 weeks in the pH range of 4.5-8.0. The proposed sensor was successfully used to determination of beryllium in mineral ore.     

Design and evaluation of a thorium (IV) selective optode

A novel optical sensor has been proposed for sensitive determination of thorium (IV) ion in aqueous solutions. The thorium sensing membrane was prepared by incorporating 4-(p-nitrophenyl azo)-pyrocatechol (NAP) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to thorium ion by changing color reversibly from yellow to red-brown in glycine buffer solution at pH 3.5. The proposed sensor displays a linear range of 8.66 × 10⁻⁶-2.00 × 10⁻⁴ M with a limit of detection of 6 × 10⁻⁶ M. The response time of the optode was about 8.8-12.5 min, depending on the concentration of Th (IV) ions. The selectivity of optode to Th (IV) ions in glycine buffer is good. The sensor can readily be regenerated by exposure to a solution mixture of sodium fluoride and 5-sulfosalicylic acid (dihydrate) (0.01 M each). The optode is fully reversible. The proposed optode was applied to the determination of thorium (IV) in environmental water samples.     

A cobalt(II)-selective PVC membrane based on a Schiff base complex of N,N′-bis(salicylidene)-3,4-diaminotoluene

A new PVC membrane electrode for Co²⁺ based on N,N′-bis(salicylidene)-3,4-diaminotoluene, an excellent neutral carrier, has been fabricated using sodium tetraphenylborate (NaTPB) as an anionic excluder and dioctylphthalte (DOP) as a solvent mediator. The electrode exhibits a linear potential response in the concentration range of 7.9 × 10⁻⁸ to 1.0 × 10⁻¹ M with a slope of 30 ± 0.2 mV per decade. The detection limit of the proposed sensor is 5.0 × 10⁻⁸ M and it can be used over a period of 5 months. The proposed sensor revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals and could be used in the pH range of 2.0-9.0. This electrode was successfully applied for the determination of Co²⁺in real samples and as an indicator electrode in potentiometric titration of cobalt ions.     

Carbon nanotube composite coated platinum electrode for detection of Cr(III) in real samples

This paper demonstrates the application of composite multi-walled carbon nanotube (MWNT) polyvinylchloride (MWNT-PVC) based on 1,5-diphenylcarbazide as chromium ionophore in potentiometric measurement. The sensor shows a good Nernstian slope of 19.52 ± 0.40 mV/decade in a wide linear range concentration of 6.3 × 10⁻⁸ to 1.0 × 10⁻² M for Cr(NO₃)₃. The detection limit of this electrode was found to be 3.2 × 10⁻⁸ M of Cr(NO₃)₃ and is applicable in a pH range of 3.0-6.8. It has a short response time of about 10 s. This chromium electrode has a good selectivity over 16 various metal ions. The practical analytical utility of this electrode was demonstrated by measurement of Cr(III) in drinking water and mineral water samples without any serious preliminary pre-treatment and chromium in multivitamin.     

Synthesis of nano-sized arsenic-imprinted polymer and its use as As selective ionophore in a potentiometric membrane electrode: Part 1

In this study, a new strategy was proposed for the preparation of As (III)-imprinted polymer by using arsenic (methacrylate)₃ as template. Precipitation polymerization was utilized to synthesize nano-sized As (III)-imprinted polymer. Methacrylic acid and ethylene glycol dimethacrylate were used as the functional monomer and cross-linking agent, respectively. In order to assembly functional monomers around As (III) ion, sodium arsenite and methacrylic acid were heated in the presence of hydroquinone, leading to arsenic (methacrylate)₃. The nano-sized As (III) selective polymer was characterized by FT-IR and scanning electron microscopy techniques (SEM). It was demonstrated that arsenic was recognized as As³⁺ by the selective cavities of the synthesized IIP. Based on the prepared polymer, the first arsenic cation selective membrane electrode was introduced. Membrane electrode was constructed by dispersion of As (III)-imprinted polymer nanoparticles in poly(vinyl chloride), plasticized with di-nonylphthalate. The IIP-modified electrode exhibited a Nernstian response (20.4 ± 0.5 mV decade⁻¹) to arsenic ion over a wide concentration range (7.0 × 10⁻⁷ to 1.0 × 10⁻¹ mol L⁻¹) with a lower detection limit of 5.0 × 10⁻⁷ mol L⁻¹. Unlike this, the non-imprinted polymer (NIP)-based membrane electrode was not sensitive to arsenic in aqueous solution. The selectivity of the developed sensor to As (III) was shown to be satisfactory. The sensor was used for arsenic determination in some real samples.