Primary amine drug sensitive electrodes based on macrocyclic polyethers with 2,2′-dinaphthyl subunits

Dinaphthyl macrocyclic polyethers were synthesized and used as neutral carriers for preparing primary amine drug sensitive PVC membrane electrodes. Contrary to the ion-associate based electrodes, which show an excellent potentiometric response to quaternary ammonium ions and the like, but a very poor response to primary amines, the macrocyclic polyether-based electrodes showed potentiometric response characteristics with primary amines preferred. Dinaphthyl macrocyclic polyether-based electrodes are superior to those based on common macrocyclic polyethers for their potentiometric selectivity coefficients much lower than those of the latter. The main characteristics of a dinaphthyl-20-crown-6-based benzyl amine sensitive electrode are as follows: linear response range, 4.2 × 10^–5 – 1.0 ×10^–1 M; slope, 51.3 mV/decade; and detection limit, 4.6 × 10^–6 M. A mexiletine sensitive electrode was prepared using dinaphthyl-23-crown-7 with following performance features: linear response range, 2.0 × 10^–5 – 1.0 ×10^–1 M; slope, 52.1mV/decade; and detection limit, 5.0 × 10^–6 M.     

Preparation and characterization of a codeine responsive electrode

Summary The behaviour of codeine reineckate and codeine tetraphenylborate membrane electrodes has been observed with a respectiveNernstian response of 58 and 56 mV/decade for 9.3×10^–5–1.3×10^–3 M codeine sulfate solutions. The workingpH ranges were 5–8 and 4–8, respectively. The selectivity towards sugars, amines, amino acids, cations, and some pharmaceutical compounds was found to be satisfactory. The isothermal temperature coefficient was 0.0014 V/°C. The electrodes were applied successfully for the determination of codeine in some pharmaceutical dosage forms with a relative standard deviation range of 0.16–0.30% and an average recovery of 98.6±0.6%.

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Herstellung und Charakterisierung einer codeinselektiven Elektrode

Zusammenfassung Das Verhalten von Codeinreineckat- und Codeintetraphenylboratmembranelektroden in 9.3×10^–5–1.3×10^–3 M Codeinsulfatlösungen wurde untersucht (Nernstscher Response: 58 bzw. 56 mV/Dekade). Der verwendetepH-Bereich für die beiden Elektroden war 5–8 bzw. 4–8. Ihre Selektivität gegenüber Zuckern, Aminen, Aminosäuren, Kationen und einigen pharmazeutisch aktiven Verbindungen ist zufriedenstellend. Der isotherme Temperaturkoeffizient beträgt 0.0014V/°C. Die Elektroden wurden erfolgreich zur Bestimmung von Codein in einigen pharmazeutischen Präparaten eingesetzt (relative Standardabweichung: 0.16–0.30%).

     

Study of a bis-furaldehyde Schiff base copper(II) complex as carrier for preparation of highly selective thiocyanate electrodes

A new highly selective thiocyanate electrode based on N,N-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD] as neutral carrier is described. The electrode has an anti-Hofmeister selectivity sequence: SCN^–>I^–>Sal^–>ClO₄ ^–>Br^–>NO₂ ^–>Cl^–>NO₃ ^–>SO₄ ^2–>SO₃ ^2–>H₂PO₄ ^– and a near-Nernstian potential linear range for thiocyanate from 1.0×10^–1 to 5.0×10^–6 mol L^–1 with a detection limit 2.0×10^–6 mol L^–1 and a slope of 57.5 mV decade^–1 in pH 5.0 of phosphate buffer solution at 20 °C. The response mechanism is discussed on the basis of results from A.C. impedance measurement and UV spectroscopy. The anti-Hofmeister behavior of the electrode results from a direct interaction between the central metal and the analyte ion and a steric effect associated with the structure of the carrier. The electrode has the advantages of simplicity, fast response, fair stability and reproducibility, and low detection limit. The selectivity of electrodes based on [Cu(II)-BFPD] exceeds that of classical anion-sensitive membrane electrodes based on ion exchangers such as lipophilic quaternary ammonium or phosphonium salts. Application of the electrode for determination of thiocyanate in waste water samples from a laboratory and a gas factory, and in human urine samples, is reported. The results obtained were fair agreement with the results obtained by HPLC.     

Tetrachloroferrate(III)-selective liquid membrane electrode based on crystal violet

An extract of crystal violet-tetrachloroferrate(III) in nitrobenzene was used to prepare a tetrachloroferrate(III)-selective liquid membrane electrode with a poly(vinyl chloride) support. The optimal conditions to determine 2.5 × 10^–5 – 5.0 × 10^–2 M iron(III) as tetrachloroferrate(III) (anionic slope 56 mV/decade, detection limit 7.9 × 10^–6 M) were found to be 4.0–5.5.M total chloride in 0.75–1.5M hydrochloric acid. The electrode was reliably applied to determine iron in human blood, haematite and mineralized vitamin syrup by direct potentiometry, standard and sample additions as well as standard subtraction techniques.     

12-Molybdophosphoric Acid as an Analytical Reagent for Greater Celandine (Celadonium) Alkaloids

The conditions for determining the total greater celandine alkaloids resulting from a plant by acid infusion were studied. The interaction between the organic cations of alkaloids and the heteropoly anion PMo₁₂O^3- ₄₀ with the formation of a sparingly soluble stable associate of total celandine alkaloids was examined using UV and IR spectroscopy and quantum-chemical calculations. The associate composition (Alk)₃PMo₁₂O₄₀ was found by amperometric titration, and the ionic solubility product was calculated to be equal to (3.0 ± 0.2) × 10^–27 at P = 0.95 and n = 5. The synthesized associate was used as an electrode-active substance in the development of an ion-selective electrode with a plasticized membrane that is reversible and selective for the organic cations of greater celandine alkaloids. Procedures for determining total alkaloids in extracts, infusions, and medicinal forms were developed using potentiometry with ion-selective electrodes and amperometric titration.     

Enhanced sensitivity electrochemical assay of low-molecular-weight heparins using rotating polyion-sensitive membrane electrodes

Use of a novel rotating polycation-sensitive polymer membrane electrode yields sensors that can serve as simple potentiometric titration endpoint detectors for the determination of three FDA approved low-molecular-weight heparin (LMWH) anticoagulant drugs (Fragmin, Normiflo, and Lovenox). The rotating electrode configuration dramatically improves the reproducibility and increases the sensitivity for LMWH determinations by protamine titration. At a rotation speed of 3000 rpm, electrodes with optimized thin (50 µm) polymer membranes doped with dinonylnaphthalene sulfonate (DNNS) respond to low levels of protamine (<2 µg mL^–1) with good precision (±1 mV, N=10), when protamine is infused continuously into a Tris-buffer solution, pH 7.4. When infusing protamine (at 5 µg min^–1) continuously into solutions containing Fragmin, a clear endpoint is obtained, with the amount of protamine required to reach this endpoint proportional to the level of Fragmin present. A detection limit of less than 0.02 U mL^–1 Fragmin can be obtained via this new method, approximately one order of magnitude lower than that previously reported based on a non-rotating polycation electrode. Similar low detection limits can be achieved for potentiometric titrations of Normiflo and Lovenox. Such titrations can also be carried out in undiluted plasma samples containing the various LMWH species. In this case, detection of the LMWHs at clinically relevant concentrations (>0.2 U mL^–1) can be readily achieved.     

Thick-film electrodes for measurement of superoxide and hydrogen peroxide based on direct protein–electrode contacts

Cytochrome c was immobilized on screen-printed thick-film gold electrodes by a self-assembly approach using mixed monolayers of mercaptoundecanoic acid and mercaptoundecanol. Cyclic voltammetry revealed quasi-reversible electrochemical behavior of the covalently fixed protein with a formal potential of +10 mV vs. Ag/AgCl. Polarized at +150 mV vs. Ag/AgCl the electrode was found to be sensitive to superoxide radicals in the range 300–1200 nmol L^–1. Compared with metal needle electrodes sensitivity and reproducibility could be improved and combined with the easiness of preparation. This allows the fabrication of disposable sensors for nanomolar superoxide concentrations. By changing the electrode potential the sensor can be switched from response to superoxide radicals to hydrogen peroxide—another reactive oxygen species. H₂O₂ sensitivity can be provided in the range 10–1000 mol L^–1 which makes the electrode suitable for oxidative stress studies.     

A copper ion-selective electrode with high selectivity prepared by sol-gel and coated wire techniques

A sol-gel electrode and a coated wire ion-selective poly(vinyl chloride) membrane, based on thiosemicarbazone as a neutral carrier, were successfully developed for the detection of Cu (II) in aqueous solutions. The sol-gel electrode and coated electrode exhibited linear response with Nernstian slopes of 29.2 and 28.1 mV per decade respectively, within the copper ion concentration ranges 1.0×10^–5–1.0×10^–1 M and 6.0×10^–6–1.0×10^–1 M for coated and sol-gel sensors. The coated and sol-gel electrodes show detection limits of 3.0×10^–6 and 6.0×10^–6 M respectively. The electrodes exhibited good selectivities for a number of alkali, alkaline earth, transition and heavy metal ions. The proposed electrodes have response times ranging from 10–50 s to achieve a 95% steady potential for Cu²⁺ concentration. The electrodes are suitable for use in aqueous solutions over a wide pH range (4–7.5). Applications of these electrodes for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu²⁺ ion using EDTA, are reported. The lifetimes of the electrodes were tested over a period of six months to investigate their stability. No significant change in the performance of the sol-gel electrode was observed over this period, but after two months the coated wire copper-selective electrode exhibited a gradual decrease in the slope. The selectivity of the sol-gel electrode was found to be better than that of the coated wire copper-selective electrode. Based on these results, a novel sol-gel copper-selective electrode is proposed for the determination of copper, and applied to real sample assays.     

Analytical applications of electrode sensitive to labetalol in pharmaceuticals

The analytical properties of an ion-selective electrode sensitive to labetalol with a liquid membrane, based on ion-pair complexes with sodium tetraphenylborate (TPB-Na⁺) are described. The studied electrode can be used for the determination of labetalol hydrochloride as a protonated form of labetalol in pharmaceuticals. The calibration curve, e.g. EMF=f(pC _LabHCl ) is linear in the range from 10⁻⁵ to 10⁻² mol L⁻¹ with a correlation coefficient of 0.9992 and slope of 61.13 mV/decade, which is close to the Nernstian slope. The detection limit of the examined electrode is 7.20×10⁻⁶ mol L⁻¹. The influence of pH of the tested solutions on the formulation of the electrode is not as considerable since the electrode works correctly in the pH range 3.0–8.0. The main attributes of the developed electrode are: stability, good reproducibility of EMF and short response time, close to 30 seconds depending on labetalol concentration in the solution. The electrode shows good selectivity for many inorganic ions. The selectivity for drug cations is weaker due to the structural similarity of the interfering cations to labetalol. The results of labetalol determination using direct potentiometry in drugs such as Pressocard (Polpharma) and Trandate (GlaxoWellcome) were compatible with the quantity of labetalol declared by the manufacturer, and with parallel UV spectrophotometric and HPLC determinations.     

Phosphoryl Containing Podands as Carriers in Plasticized Membrane Electrodes Selective to Quaternary Ammonium Surfactants

Open chain polyethers with phosphoryl-containing terminal groups have been studied as carriers in plasticized membrane electrodes that are selective towards cationic surfactants. Host–guest complexation has also been studied by means of batch extraction and bulk membrane transport experiments. For the various guests, the bulk membrane (chloroform) transport rate decreases in the series tetraalkyl ammonium > alkyl pyridinium > alkyl ammonium, while the series of solvent extraction efficiency is exactly opposite; an explanation for this behaviour is proposed. The performance of electrode membranes follows the series for bulk membrane transport. Among the ISE membranes of various composition, one containing the longest (seven oxygen atoms) podand, o-nitrophenyl octyl ether (plasticizer), and sodium tetraphenyl borate (anionic additive) performs the best. The slope of the electrode function equals 58.5 mV/decade, the detection limit for dodecyltrimethylammonium is 3.2 × 10^-6 M. ISE response time is 5–10 s, the working pH range is 2–11 and lifetime is at least 6 months. The electrode selectivity is significantly better than that of conventional ion-association and crown ether based electrodes.     

A highly sensitive PVC membrane iodide electrode based on complexes of mercury(II) as neutral carrier

A novel solvent polymeric membrane electrode based on bis(1,3,4-thiadiazole) complexes of Hg(II) is described which has excellent selectivity and sensitivity toward iodide ion. The electrode, containing 1,4-bis(5-methyl-1,3,4-thiadiazole-2-yl-thio)butanemercury(II) [Hg(II)BMTB(NO₃)₄], has a Nernstian potentiometric response from 2.0×10^–8 to 2.0×10^–2 mol L^–1 with a detection limit of 8.0×10^–9 mol L^–1 and a slope of –59.0±0.5 mV/decade in 0.01 mol L^–1 phosphate buffer solution (pH 3.0, 20°C). The selectivity sequence observed is iodide>bromide>thiocyanate>nitrite>nitrate>chloride>perchlorate>acetate>sulfate. The selectivity behavior is discussed in terms of the UV–Vis spectrum, and the process of transfer of iodide across the membrane interface is investigated by use of the AC impedance technique. The electrode was successfully applied to the determination of iodide in Jialing River and Spring in Jinyun Mountains, with satisfactory results.     

Electrodeposition of Lu on W and Al electrodes: Electrochemical formation of Lu–Al alloys and oxoacidity reactions of Lu(III) in the eutectic LiCl–KCl

The electrodeposition of lutetium on inert electrodes and the formation of lutetium–aluminium alloys were investigated in the eutectic LiCl–KCl in the temperature range 673–823 K. On a tungsten electrode, the electroreduction of Lu(III) proceeds in a single step and electrocrystalization plays an important role. Experimental current–time transients are in good agreement with theoretical models based on either instantaneous or progressive nucleation with three dimensional growth of the nuclei, depending on the working temperature. The diffusion coefficient of Lu(III) was determined by chronopotentiometry by applying the Sand equation. The activation energy for diffusion was found to be 31.5 ± 1.3 kJ mol⁻¹. Al₃Lu and mixtures of Al₃Lu and Al₂Lu, characterized by XRD analysis and SEM, were obtained from the LiCl–KCl melt containing Lu(III) by potentiostatic electrolysis using an Al electrode. The activity of Lu and the standard Gibbs energies of formation for Al₃Lu were estimated from open-circuit chronopotentiometric measurements. The E–pO²⁻(potential–oxoacidity) diagram for Lu–O stable compounds in LiCl–KCl at 723 K has been constructed by combining theoretical and experimental data. In this way, the apparent standard potential for the Lu(III)/Lu system has been determined by potentiometry. Potentiometric titrations of Lu(III) solutions with oxide donors, using a yttria stabilized zirconia membrane electrode “YSZME” as a pO²⁻ indicator electrode, have shown the stability of LuOCl and Lu₂O₃ in the melt and their solubility products have been determined at 723 K.     

Coated,Wire-Based,New Schiff Base Potentiometric Sensor for Lead(II) Ion

An ion-selective electrode for lead(II) based on a dispersion of N,N"-bis(3-methyl salicylidine)-p-phenyl methane diamine particles into a polymeric membrane using coated-wire configuration is described. Membranes based on polyvinyl chloride containing different amounts of plasticizer and ionophore are studied. The best performance in terms of slope (30.3 ± 0.6 mV per decade) and response time (<15 s) is displayed. The sensor shows a Nernstian response for Pb(II) ions over a wide concentration range of 2.0 × 10^–5 to 0.10 M. The sensors can be used for more than three months without any considerable divergence in potentials. The selectivity is also good towards the most common univalent and divalent cations and the signal is constant in the pH range 1.6–6.0. An application to lead determination in mineral rocks and wastewater proved to be a success, and it was employed as an indicator electrode in potentiometric titration of CrO^2– ₄ with lead ions.     

A miniature enzyme electrode sensitive to urea

Summary Miniature enzyme electrodes sensitive to urea have been made with tip diameters ranging from 50 to 500m by immobilizing the enzyme urease on the tip of an antimony electrode. These electrodes give a linear response in the concentration range of 1.0×10^–4-1.0×10^–2 M urea with a slope of 40–45 mV per decade change in concentration. The response time of these electrodes is less than 1 min and the wash time is 1–2 min. This type of electrode has a minimum life time of 3 months.

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Eine kleine, harnstoffempfindliche Enzymelektrode

Zusammenfassung Harnstoff-sensitive Enzymelektroden mit Spitzendurchmessern zwischen 50 und 500m wurden durch Immobilisierung des Enzyms Urease auf der Spitze einer Antimon-Elektrode hergestellt. Diese Elektroden verhielten sich linear im Konzentrationsbereich 1,0×10^–4–1,0×10^–2 M, und hatten eine Steigerung von 40–45 mV pro Dekade der Konzentrationsänderung. Die Antwortzeit dieser Elektroden liegt unter 1 min und die Auswaschzeit beträgt l–2 min. Diese Art Elektroden hat eine Lebensdauer von mehr als 3 Monaten.

     

Interaction of Gadolinium(III) with Nitrilotrimethylenephosphonic Acid

Interaction of gadolinium(III) with nitrilotrimethylenephosphonic acid is studied by potentiometry in wide range of concentration ratios and pH at 298.15 K and ionic strength of 0.1 (KNO₃). Logarithmic constants of protonation (logK _pr) are 7.88 ± 0.08 and 4.93 ± 0.05 for GdL^3– and GdHL^2–, respectively.     

A double-membrane nitrate ion-selective electrode based on aliquat-nitrate in paraffin

Summary A double-membrane nitrate-selective electrode [as a modified coated wire electrode (CWE)] was prepared with an internal conductor membrane made of tetrabutylammonium bromide (BrTBA) in naphthalene, and an external active membrane (Aliquat-NO ₃ ^– in paraffin), on an Agamalgamated electrode. The nitrate-electrode exhibits linear Nernstian response over the range 1 to 10^–4.5 mol/l of nitrate, with a slope of 56.01 ± 0.9 mV decade^–1. The selectivity coefficients for 17 ions were calculated. The effects of pH, membrane composition and thickness were also studied. The life-time of the electrode is 15 days and the stability of its potential is 0.6 mV/12 h. The electrode was preserved dry because of the better sensitivity, range of linear response and detection limit attained. The determination of nitrates in waters and fertilizers was also attemped with this electrode, using the interpolation and standard-addition methods.

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Nitrationenselektive Doppelmembranelektrode aufgrund von Aliquat-Nitrat in Paraffin

     

Transport properties and electroanalytical response characteristics of drotaverine ion-selective sensors

The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10^–6 to 5×10^–2 mol L^–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10^–6 mol L^–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography.     

Anion recognition through amide-based dendritic molecule: a poly(vinyl chloride) based sensor for nitrate ion

Poly(vinyl chloride) (PVC)-based membranes of N,N-bis-succinamide-based dendritic molecule with tetrabutyl ammonium bromide (TBAB) as a cation inhibitor and dibutylphthalate (DBP), dioctylphthalate (DOP), dibutyl (butyl) phosphonate (DBBP) and 1-chloronaphthalene (CN) as plasticizing solvent mediators were prepared and used as nitrate ion-selective electrodes. Optimum performance was observed with the membrane having I-PVC-TBAB-DBP in the ratio 1:33:1:65 (w/w). The electrode has a linear response to nitrate with a detection limit of 3.9 × 10⁻⁵ ± 0.07 M and Nernstian compliance (57.0 ± 0.2 mV/decade) between pH 2.8 and 9.6 with a fast response time of about 20 s. The selectivity coefficient values of the order of 0.001 for mono-; bi- and trivalent anions; indicate high selectivity for nitrate ions over these anions. The preparation procedure of the electrode is very easy and inexpensive. The electrodes were used over a period of 45 days with good reproducibility. The analytical usefulness of the proposed electrode has been evaluated by its application in the determination of nitrate ions in waste water samples.     

A New PVC-Membrane Electrode Based on a Macrocyclic Ionophore for Selective Determination of Ni (II) Ions

A poly(vinyl chloride)-based membrane of 3,4:12,13-dibenzo-1,6,10,15-tetraazacyclooctadecane with sodium tetraphenyl borate (NaTPB) as an anion excluder and dibutylphthalate (DBP), dibutylbutylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEHP) and tributyl phosphate (TBP) as plasticizing solvent mediator was prepared and investigated as a Ni(II)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-TEHP-NaTPB composition 1:4:1:1, which worked well over a wide concentration range (2.82 ×10⁻⁶−1.00 × 10⁻¹ M) with a Nernstian slope of 30.5 mV per decade of activity between pH 2.5–7.5. This electrode showed a fast response time of 18 s and was used over a period of 4 months with good reproducibility (S=0.4 mV). The selectivity coefficient over mono-, di- and trivalent cations indicate excellent selectivity for Ni (II) ions over a large number of cations. Anions such as Cl⁻ and NO₃⁻ do not interfere and the electrode also works satisfactorily in a partially non-aqueous medium. It has been used successfully for determination of Ni (II) in real samples.     

Anodic Dissolution of Gold in Cyanide Solutions Containing Lead Ions: Effect of the Solution pH

The effect of the electrode potential on the gold dissolution rate in alkali–cyanide solutions with and without 10^–5 M of hydroxy compounds of lead is studied. With the compounds, the process rate passes through a maximum, whose potential E _m shifts in the negative direction and whose height drops with increasing pH. The pH dependence of E _m is linear, with the slope dE _m/dpH = –71 ± 5 mV, and correlates with that of the potential at which lead adatoms start to undergo desorption from the gold surface in alkali solutions. Without the compounds, the gold dissolution rate in alkali–cyanide solutions is independent of the solution pH at E < 0. Thus, the effect of the solution pH in this potential range is connected not with a direct participation of hydroxide ions in the anodic process but is of a secondary nature caused by the dependence of the region of adsorption of catalytically active lead adatoms on the hydroxide ion content in solution.