Polymeric liquid membrane electrodes incorporated with macrocyclic hexaamines for screening adenine nucleotides

Lipophilic macrocyclic hexaamines supported by a poly(vinyl chloride) PVC matrix were used for the construction of liquid membrane electrodes sensitive toward adenine nucleotide polyanions. The membrane potential strongly depended on the pH of the sample solution. This phenomenon occurs due to the ability of the ionophore to accept protons. Therefore, the optimum pH was determined based on potential pH profile. The potential measurements were carried out at pH 6.0 in the presence of 10(-2) M 2-[N-morpholino] ethanesulfonic acid (MES) buffer. The potential response of these electrodes toward ATP(-4) and/or HATP(-3) was close to the Nernstian slope. The selectivities against ADP(-3), AMP(-2), HPO(4)(-2), and monovalent inorganic anions were estimated using the matched potential method. Chloride ions slightly affected potential response of the electrodes toward ATP(-4)/HATP(-3). The influence of ionophore chemical structure on the selectivity and the sensitivity of these electrodes is briefly discussed.     

Hydrogen ion-selective membrane electrodes based on alkyldibenzylamines as neutral carriers

New synthetic hydrogen ion-selective carriers, derivatives of dibenzylamine, have been used as neutral carriers in liquid membrane electrodes to measure pH range from 2 to 10. A H(+)-selective membrane electrode based on octyldibenzylamine gave a better linear response to pH than other alkyldibenzylamines as neutral carriers. It gave a linear response over the pH range 2-10 and a slope of 56.5 mV/pH at 20 degrees C. The electrode had fairly low electrical resistance, good potential stability and reproducibility. The selectivity coefficients towards sodium, potassium and calcium ions as well as other characteristics of the membrane electrode have been studied.     

Solid-state ion-selective electrodes for the potentiometric determination of phosphate

A number of solid-state ion-selective electrodes for the potentiometric determination of phosphate have been made and their properties investigated. The most successful of these electrodes, which had a membrane comprising silver sulphide, lead sulphide and lead hydrogen phosphate, had a theoretical Nernstian response to orthophosphate ion at concentrations down to 5 mug/ml total phosphate at pH 8.3. The electrode had a slow response and its standard potential changed with time. Anions such as sulphate, bicarbonate and nitrate did not interfere; chloride had a transient effect, but even at its worst the interference was less serious than with other phosphate electrodes. The electrode was used as an indicator in the potentiometric precipitation titration of phosphate and lanthanum.     

Iodide‐Selective Electrodes Based on Bis[N(2‐methyl‐phenyl) 4‐Nitro‐thiobenzamidato]mercury(II) and Bis[N‐phenyl 3,5‐Dinitro‐thiobenzamidato]mercury(II) Carriers

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on recently synthesized mercury complexes including Hg(Nmpntb)₂ and Hg(Npdntb)₂ as new carriers for iodide‐selective electrodes by incorporating the membrane ingredients on the surface of graphite electrodes are reported. The effect of various parameters including the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses toward iodide over a wide concentration range of 7×10^?7 to 0.1 M and 1×10^?6 to 0.1 M, with slopes of 59.6±0.8 and 58.9±0.9 mV per decade of iodide concentration and detection limit of 3×10^?7 M and 7×10^?7 for Hg(Npdntb)₂ and Hg(Nmpntb)₂, respectively, over a wide pH range of 3–11. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show good ability to discriminate iodide over several inorganic and organic anions. The electrodes were successfully applied to direct determination of iodide in synthetic mixture, waste water and drinking water and as indicator electrodes in precipitation titrations.     

Bis(2-mercaptobenzoxazolato)mercury(II) and bis(2-pyridinethiolato)mercury(II) complexes as carriers for thiocyanate selective electrodes

Highly selective poly(vinyl chloride) (PVC) membrane electrodes based on bis(2-mercaptobenzoxazolato)mercury(II) [Hg(MBO)₂] and bis(2-pyridinethiolato)mercury(II) [Hg(PT)₂] complexes as new carriers for thiocyanate-selective electrodes are reported. The electrodes were prepared by coating the membrane solution containing PVC, plasticizer, carriers and additives on the surface of graphite electrodes. Influence of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. Both sensors exhibited Nernstian responses towards thiocyanate over a wide concentration range of 1×10⁻⁶ to 0.1 M, with slopes of 60.6±0.8 and 57.5±1.2 mV per decade of thiocyanate concentration for Hg(MBO)₂ and Hg(PT)₂ carriers, respectively, over a wide pH range of 3-11. The limit of detection for both electrodes was ∼6×10⁻⁷ M. The sensors have response times of ≤5 s and can be used for at least 2 months without any considerable divergence in their potential response. The proposed electrodes show fairly good discrimination of thiocyanate over several inorganic and organic anions. The electrodes were successfully applied to direct determination of thiocyanate in saliva and as indicator electrodes in precipitation titrations.     

溶剂聚合膜pH电极作内电极的气敏电极的研究

研究了以中性载体为活性物的石墨内导平头溶剂聚合膜(SPM)pH电极作内电极的二氧化碳和氨气敏电极。电极的性能取决于中性载体的特性,其中以菸酸十八酯为内电极膜活性物的二氧化碳气敏电极和以二辛基十八胺为活性物的氨气敏电极性能较佳。二氧化碳气敏电极用作丙酮酸脱羧酶酶电极的原电极,其性能院于传统的以玻璃pH电极作内电极的二氧化碳气敏电极。     

Potentiometric determination of neodymium (III) ions using tin (IV) antimonotungstate and zirconium (IV) antimonotungstate as electro-active materials

Neodymium (III)-selective electrodes have been prepared by using tin (IV) antimonotungstate (SnSbW) and zirconium (IV) antimonotungstate (ZrSbW) as electro-active materials and epoxy resin as a binding material. In the case of SnSbW, best performance is exhibited by a membrane having the composition: tin (IV) antimonotungstate (50%) and epoxy resin (50%). It shows excellent response in the concentration range of 10^–4?M to 10^–1?M Nd (III) ion with a super-Nernstian slope of 40.0?mV/decade. It has a fast response time of 20 seconds and can be used for at least six months without any considerable divergence in potential. In the case of ZrSbW, best performance is exhibited by a membrane having the composition: zirconium (IV) antimonotungstate (40%) and epoxy resin (60%). It shows excellent response in the concentration range of 10^–5?M to 10^–1?M Nd (III) ion with a near-Nernstian slope of 25.0?mV/decade. It has a fast response time of 10 seconds and can be used for at least six months without any considerable divergence in potential. Effect of internal solution has been studied and the electrode was successfully used in partially non-aqueous medium, too. Selectivity coefficients have been determined by FIM method, with respect to alkali, alkaline earth, some transition and rare earth metal ions. ZrSbW electrode can be used in the pH range of 2.9–9.9 and SnSbW shows pH range 3.0–9.0. Both the electrodes have been used as indicator electrodes in the potentiometric titration of Nd (III) ions against EDTA.     

Description of the Effects of Non‐ion‐exchange Extraction and Intra‐membrane Interactions on the Ion‐selective Electrodes Response within the Interface Equilibria‐triggered Model

The recently proposed interface equilibria‐triggered dynamic diffusion model of the boundary potential has proven its high predictive efficiency for quantification of the ion exchange and co‐extraction effects at the interface, as well as of the trans‐membrane transfer effect, on the electrode response. It is applicable for both ion exchanger‐based and neutral carrier‐based electrodes. In this communication, the adaptability of this model to more complex cases, when non‐ion‐exchange extraction processes at the interface (partition of organic acids’ and bases’ molecular forms and extraction of ionic associates) are coupled with protolytic equilibria in the aqueous phase and with self‐solvation process in the membrane phase, is demonstrated. By the example of electrodes reversible to ions of highly lipophilic physiologically active bases and acids (amiodarone, verapamil, vinpocetine, salicylic acid), it is shown that the peculiarities of their functioning, such as a very strong pH effect on the potential of cation‐selective electrodes, non‐monotonic pH dependence of the potential and super‐Nernstian response slope in certain pH region for a salicylate‐selective electrode, are well described within the model.     

New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores

Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd(2+) was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd(2+). The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg(-1)) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4±0.6 mV decade(-1) of activity for Cd(2+) ions and a working concentration range of 1.6×10(-6)-1.0×10(-2)M. The sensor has a fast response time of 10s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed as a probe for determining Cd(2+) from the oxidation of CdS QDs solution and the real treatment waste water sample with excellent results.     

Application of cell-based biosensors for the detection of bacterial elicitor flagellin

Cell-based biosensors, bioelectronic portable devices containing plant living cells have been used for monitoring some physiological changes induced by pathogen-derived signal molecules called flagellin. The screen-printed electrodes have been adapted for preparation of biosensors. The proton-sensitive thick films have been printed using composite bulk modified with edition of RuO(2). Obtained disposable electrodes were made possible to measure the pH change with well sensitivity and reproducibility. Tobacco cells attached to the electrode surface, cell-based biosensor, can be used for the detection of flagellin, the virulence factor of bacterial pathogen. We culture tobacco cells on the surface of such electrotransducer for several weeks and monitor of potential of cells under flagellin stimulation. The detection of the electrochemical proton gradient across the plasma membrane serves as the analytical signal. The electrode response depended upon H(+) concentration in extracellular solution. It can be conveniently observed on the surfaces of biosensors. Suitable stability and the good response time of constructed biosensors were observed. Future development of these cell-based biosensors could draw advances in selective monitoring of microbial pathogens and other physiologically active components. Moreover, this new method is much faster compared with the traditional microbial testing.     

Aromatic sulphonate ion-selective electrode membrane with crystal violet as ion-exchange site

Four triphenylmethane derivatives (cations) and a high molecular-weight quaternary ammonium ion were used as the ion-exchange site in the liquid membranes of electrodes responsive to aromatic sulphonate ions, such as benzenesulphonate and alpha-naphthalenesulphonate. The nitrobenzene or 1,2-dichloroethane membrane containing the Crystal Violet-aromatic sulphonate pair had good sensitivity, showing an approximately Nernstian response down to 10(-4)M sulphonate. The potential of the Crystal Violet membrane was independent of pH variation from 2.5 to 12. Chloride and sulphate ions in the aqueous sample solution did not affect the electrode potential. 1,3,6-Naphthalenetrisulphonate exerted essentially no influence on the potential of the alpha-naphthalenesulphonate electrode. The interference of the nitrate ion was relatively large. The conductivity and association of the solute species in the membrane were estimated.     

Anion selective polymeric membrane electrodes based on cyclopalladated amine complexes

The potentiometric anion selectivity of two polymer membrane based electrodes (I and II) formulated with two new cyclopalladated amine complexes as the active components are examined. The electrodes exhibit a non-Hofmeister selectivity pattern with a significantly enhanced response towards thiocyanate, iodide and nitrite. The graph potential versus log c is linear over the concentration range 10(-6)-6x10(-2) M thiocyanate with electrode I and 10(-6)-10(-3) M with electrode II; 10(-5)-10(-2) M iodide with electrode I and 10(-3)-6x10(-2) M with electrode II; and 10(-3)-6x10(-2) M nitrite with both electrodes. The influence of the plasticizer and pH are studied. The potentiometric selectivity coefficients for I, II and blank membrane electrodes are reported. The selective interaction between Pd(II) thiocyanate, iodide and nitrite is postulated to be the reason for its higher response.     

Effects of ion-carrier substituents on the potentiometric-response characteristics in anion-selective membrane electrodes based on iron porphyrins.

The potentiometric response characteristics with respect to salicylate anion of several membrane electrodes based on iron(III) tetraphenylporphyrin chloride (FeTPPCl) and derivatives with electrophilic and nucleophilic substituents, incorporated into plasticized polyvinylchloride (PVC) membranes were investigated. Complexes tetraphenyl porphyrin iron(III) chloride (FeTPPCl; A), tetrakis (4-methoxyphenyl) porphyrin iron(III) chloride (Fe(TOCH3PP)Cl; B), tetrakis (2,6-dichlorophenyl) porphyrin iron(III) chloride (Fe(TDClPP)Cl; C), tetrakis (4-nitrophenyl) porphyrin iron(III) chloride (Fe(TNO2PP)Cl; D), and tetrakis (pentafluorophenyl) porphyrin iron(III) chloride (Fe(TPFPP)Cl; E) were used as anion carriers in the membrane electrodes. The sensitivity, working range, detection limit, response mechanism, and selectivity of the membrane sensor toward interference shows a considerable dependence on the type of carrier substituent and the pH value of the sample solution. Potentiometric investigations in solutions of various pH show that the carrier complex containing fluoro substituents (E), which have very strong electron-accepting properties and a high ability to form hydrogen bonds, is capable of serving as a positively charged ionophore. Some other ionophores are capable of serving as both charged and neutral carriers under different conditions. The electrodes prepared in this work show super-Nernstian slopes with respect to salicylate concentration, which tend to a Nernstian response (slope near to -59 mV decade-1) upon an increase of the pH of the test solution. The results of UV/Vis absorption spectroscopy are used for interpretation of the formation of an oxene complex between salicylate and iron porphyrins.     

All-solid-state potentiometric sensors for ascorbic acid by using a screen-printed compatible solid contact

The development of all-solid-state potentiometric ion selective electrodes for monitoring of ascorbic acid, by using a screen-printed compatible solid contact is described. The applied methodology is based on the use of PVC membrane modified with some firstly-tested ionophores (triphenyltin(IV)chloride, triphenyltin(IV)hydroxide and palmitoyl-l-ascorbic acid) and a novel one synthesized in our laboratory (dibutyltin(IV) diascorbate). Synthesis protocol and some preliminary identification studies are given. A conductive graphite-based polymer thick film ink was used as an internal solid contact between the graphite electrode and the PVC membrane. The presence and the nature of the solid contact (plain or doped with lanthanum 2,6-dichlorophenolindophenol (DCPI)) seem to enhance the analytical performance of the electrodes in terms of sensitivity, dynamic range, and response time. The analytical performance of the constructed electrodes was evaluated with potentiometry, constant-current chronopotentiometry and electrochemical impedance spectroscopy (EIS). The interference effect of various compounds was also tested. The potential response of the optimized Ph₃SnCl-based electrode was linear against ascorbic acid concentration range 0.005-5.0 mM. The applicability of the proposed sensors in real samples was also tested. The detection limit was 0.002 mM ascorbic acid (50 mM phosphate, pH 5 in 50 mM KCl). The slope of the electrodes was super-Nernstian and pH dependent, indicating a mechanism involving a combination of charge transfer and ion exchange processes. Fabrication of screen-printed ascorbate ISEs has also been demonstrated.     

Calcium-selective electrodes with pvc membranes and solid internal contacts

The response of calcium-selective electrodes based on PVC membranes has been investigated. The membrane, containing the calcium salt of di-n-octylphenylphosphoric acid, is in direct contact with the internal electrode made of silver, silver/silver chloride, or teflonized graphite. Evidence is given to support the hypothesis that the oxygen half-cell is responsible for the potential at the solid contact—membrane interface. Silver or teflonized graphite contacts provide better potential stability and analytical sensitivity than Ag/AgCl contacts. The electrodes can be used for determination of calcium in waters.     

Fabrication of Membrane Sensitive Electrodes for the Validated Electrochemical Quantification of Anti-Osteoporotic Drug Residues in Pharmaceutical Industrial Wastewater

Accurate and precise application of ion-selective electrodes (ISEs) in the quantification of environmental pollutants is a strenuous task. In this work, the electrochemical response of alendronate sodium trihydrate (ALN) was evaluated by the fabrication of two sensitive and delicate membrane electrodes, viz. polyvinyl chloride (PVC) and glassy carbon (GC) electrodes. A linear response was obtained at concentrations from 1 × 10⁻⁵ to 1 × 10⁻² M for both electrodes. A Nernstian slope of 29 mV/decade over a pH range of 8–11 for the PVC and GC membrane electrodes was obtained. All assay settings were carefully adjusted to obtain the best electrochemical response. The proposed technique was effectively applied for the quantification of ALN in pure form and wastewater samples, acquired from manufacturing industries. The proposed electrodes were effectively used for the determination of ALN in real wastewater samples without any prior treatment. The current findings guarantee the applicability of the fabricated ISEs for the environmental monitoring of ALN.     

Polymer membrane sensors for sildenafil citrate (Viagra) determination in pharmaceutical preparations

The construction and performance characteristics of ion selective membrane electrodes for sildenafil citrate (SC) drug (the active component of Viagra) are described. The proposed sensors are based on the formation of the complex ion associates of SC with sodium tetraphenylborate (SC-TPB) and phosphomolybdic acid (SC-PMA) as ionophores in poly vinyl chloride membrane (PVC). Both electrodes SC-PMA and SC-TPB showed a linear and stable potential response with near-Nernstian slope of 55.5±0.35 and 53.5±0.3 mV per decade over a wide range of concentration 10⁻² to 10⁻⁵ M sildenafil with good reproducibility, respectively. The electrodes showed a fast response time of 30 and 40 s. and were used over a wide range of pH 3-6. The selectivity coefficients indicated good selectivity for SC drug over a large number of nitrogenous compounds and some inorganic cations. The proposed sensors are tested for the analysis of SC in pure form, pharmaceutical preparations and blood serum. An average recovery of 98.9-99.5±0.6% and correlation to the existing methods of 0.998 were achieved.     

Selective Liquid and (Vinyl-Chloride) Pentoxyverine Membrane Electrodes - Their Preparation and Use for the Potentiometric Determination of Pentoxyverine Citrate

Abstract

The use of liquid and poly(vinyl-chloride) membrane electrodes which are sensitive and reasonably selective for pentoxyverine determination is described here. The electrodes are based on the use of pentoxyverine-picrate, pentoxyverine-picrolonate and pentoxyverine-tetraphenylborate ion association complexes as electroactive materials in nitrobenzene or in poly(vinyl chloride) matrix. These electrodes show near Nernstian response values in different concentration ranges, depending on the nature of the used counter-ions, at 3.3–7.8 pH range. Potentiometric determination of pentoxyverine citrate with use of these electrodes gives good results which later on are compared with those obtained by non-aqueous titration.     

Coated wire ion-selective electrode for palladium(II) and its application to catalyst analysis

The construction, performance and application of polymeric membrane (PME) and coated wire (CWE) palladium(II)-selective electrodes based on the ion pair between tetra bromopalladate(II) and hexadecylpyridinium cation (HDP⁺) in a poly(vinyl chloride) matrix, plasticized with o-NPOE are described. The influence of membrane composition, bromide ion concentration and pH on the potentiometric responses of electrodes were investigated. Nernstian responses were obtained for the two type of electrodes with low limits of detection (1.0×10⁻⁶ M for PME and 5.0×10⁻⁸ M for CWE). The potentiometric responses are independent of the pH of test solution in the range 3–8. The response time of electrodes are fast (30 s for PME and 10 s for CWE), and they can be used for at least 3 months without any considerable divergence in potentials. The proposed electrodes revealed good selectivity for palladium(II) respect to different cations and anions. They were used to the direct potentiometric determination of palladium(II) in silicon-alumina catalysts.     

Liquid and poly (vinyl chloride) matrix membrane electrodes for the selective determination of cocaine in illicit powders

The construction of liquid membrane and PVC matrix-type cocainium ion selective electrodes and their use for direct potentiometry and potentiometric titration of cocaine are described. The ion-pair complexes of cocaine cation with reineckate and tetraphenylborate anions are either dissolved in nitrobenzene solvent or dispersed in a PVC matrix, with DOP or DBS plasticizer, and used as the ion-exchange membranes. The electrochemical response characteristics of electrodes incorporating these types of membranes are evaluated with regard to the effect of pH, foreign basic compounds, temperature and gamma-radiation. The electrodes display a stable fast Nernstian response for 10(-2)-10(-5)M cocainium cation over the pH range 3-7, the lower limit of detection being 1 mug/ml. Determination of as low as 20 mug/ml cocaine hydrochloride shows an average recovery of 98% and a mean standard deviation of +/-0.6%. The electrodes exhibit useful analytical characteristics for determining cocaine in some illicit powders. The results agree fairly well with those obtained by gas-liquid chromatography.