Ion-selective electrodes for basic drugs

Coated-wire ion-selective electrodes based on dinonylnaphthalene sulfonic acid (DNNS) are prepared for methadone, methylamphetamine, cocaine and protriptyline in protonated form. In each set, nearly-Nernstian responses are obtained while detection limits range from 10^-5.5M for cocaine and methylamphetamine electrodes, to 10^-6.0M for methadone, and 10^-6.5 M for protriptyline electrodes. Selectivity is found to decrease in the order methadone, protriptyline, cocaine and methylamphetamine; these results are consistent with systematic selectivity studies reported earlier for electrodes in this family.     

Ion-selective electrodes for determination of organic ammonium ions: Ways for selectivity control

The influence of the ISE membrane composition on the selectivity for primary, secondary, tertiary, and quaternary alkylammonium cations, as well as for cations of physiologically active amines, has been investigated. Factors studied include the effect of plasticizer (2-nitrophenyl octyl ether, o-NPOE; dibutyl phthalate, DBP; dinonyl adipate, DNA; tris(2-ethylhexyl) phosphate, TEHP) and ion exchanger (potassium tetrakis(4-chlorophenyl)borate, K(TpClPB); potassium tris(nonyloxy)benzenesulfonate, K(TNOBS)), as well as that of the lipophilic cationic additive (tetradecylammonium nitrate, (TDA)NO(3)) and neutral carrier (dibenzo-18-crown-6) presence in membrane. It has been established that plasticizer nature affects K(i,j)(pot) values both when the target and/or foreign ions have non-ionic polar groups capable of specific interaction with plasticizer, and when the only difference consists in the substitution degree of their ionic groups. K(i,j)(pot) values for quaternary alkylammonium cations over primary-tertiary ones change in the following order: TEHP>DBP approximately DNA>o-NPOE. The highest K(i,j)(pot) value change is achieved for the primary-quaternary alkylammonium cation pair, amounting to 3 and 4.7 orders for membranes containing K(TNOBS) and K(TpClPB) as ion exchangers, respectively. In its turn, the ion exchanger influence on the selectivity depends on plasticizer nature, it being maximal for o-NPOE (about 2 orders) and practically non-existent for TEHP. On the whole, as compared to K(TpClPB)-based ISEs, those based on K(TNOBS) show higher selectivity for primary-tertiary alkylammonium cations over quaternary ones. Incorporation of (TDA)NO(3) into membrane causes further improvement of selectivity for primary-tertiary alkylammonium cations in the case of K(TNOBS) only. The maximal total effect of the ion exchanger and lipophilic ionic additive is observed for ISEs with DNA-plasticized membranes and is over 3 orders. The influence of crown ether on the selectivity also depends significantly upon ion exchanger and plasticizer nature. For ISEs with o-NPOE-plasticized membranes the K(i,j)(pot) value changes can be as great as 3 (ion exchanger K(TNOBS)) and even 4.5 (ion exchanger K(TpClPB)) orders. On the contrary, for ISEs with TEHP-plasticized membranes the crown ether effect on the selectivity is unessential. The results obtained are explained by peculiarities of organic ammonium cations solvating by plasticizer and association of cations with ion exchangers.     

Ion-selective electrodes in titrations involving azo-coupling reactions

An organic cation-selective indicator electrode based on a PVC membrane plasticized with 2-nitrophenyl 2-ethylhexyl ether can be used in potentiometric titrations of aromatic hydroxy compounds, amines, and compounds containing active methylene groups, with 4-methyl-, 4-bromo-, or 4-nitro-benzenediazonium chloride solutions as titrants. Useful results were obtained in determinations of 16 passive components, including 2-naphthol, some 2-naphthol sulfonic acids, 8-quinolinol and its 5-sulfonic acid, ammo-1-naphthol-3-sulfonic acids, 1-naphthylamine sulfonic acids, resorcinol, 2,4-toluylenediamine, two acetanilide derivatives, and two substituted sulfophenyl pyrazolone derivatives. 4-Bromobenzenediazonium chloride proved to be the best titrant of the diazonium salts tested.     

Ion-selective electrodes in titrations involving azo-coupling reactions

Compounds that react slowly with arenediazonium salts can be determined by back-titration. When 1-naphthalene- or 4-bromo-1-naphthalenendiazonium chloride is used, the excess is back-titrated with sodium tetraphenlborate or 2,4-diaminotoluene, the titration being monitored with a PVC membrane electrode plasticized with 2-nitrophenyl 2-ethylhexyl ether. Disodium 2-naphthol-3,6-disulfonate (r-salt), 2-naphthol-7-sulfonic acid, acetylacetone, and 1-(2′,5′-dichloro-4′-sulfophenyl)-3-carboxy-5-pyrazolone were determined without xyxtematic errors in times shorter than needed for direct titration.     

Ion-selective electrodes in organic functional group analysis: Microdetermination of hydrazines with the copper electrode

Summary A simple micromethod is described for the determination of hydrazines using the copper ion-selective electrode. The method is based on direct potentiometric titration of the sample in ammoniacal solution of pH 9.5±0.2 with copper(II) ions at room temperature. N-Shaped curves with well-defined inflections at 11 and 12 molar ratios are obtained. This is probably due to the formation of copper monohydrazinate and copper dihydrazinate complexes. Various alkyl and aryl hydrazines and hydrazine salts have been satisfactorily analyzed with an average recovery of 99.4% and a relative standard deviation of ±0.4%. The reaction of hydrazines with Fehling's solution followed by measuring the copper(I) oxide formed using the copper ion-selective electrode also has been investigated.

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Zusammenfassung Eine einfache Mikromethode zur Bestimmung von Hydrazinen mit einer kupferionen-selektiven Elektrode wurde beschrieben. Sie beruht auf der direkten potentiometrischen Titration in ammoniakalischer Lösung mit Cu(II)ionen bei pH 9,5±0,2 bei Zimmertemperatur. N-förmige Kurven mit gut ausgebildeten Spitzen bei Molverhältnissen 11 und 12 wurden erhalten, wahrscheinlich auf Grund der Bildung von Mono- bzw. Dihydrazinatkomplexen des Kupfers. Verschiedene Alkyl- und Arylhydrazine und deren Salze wurden zu 99,4% mit einer Standardabweichung von ±0,4% wiedergefunden. Die Reaktion der Hydrazine mit Fehlingscher Lösung wurde ebenfalls durch Messung des entstandenen Cu(I) mit der erwähnten Elektrode untersucht.

     

Ion-selective electrodes and enzyme electrodes in environmental and clinical studies.

Electrodes have been developed for the assay of glucose, urea, amino acids, uric acid, phosphate, nitrate and perchlorate. The electrodes for the organic compounds are enzyme electrodes which are prepared by chemically immobilizing an enzyme over the outside of a conventional ion-selective electrode. These electrodes will be discussed in depth. The progress and the development of the electrodes that show sensitivity and selectivity for phosphate, nitrate and perchlorate will be outlined. The basis of these sensors is a complex of a transition metal of either an analog of thiourea or an organic chelator, such as 1,10-phenanthraline. Such electrodes respond linearly to phosphate, nitrate or perchlorate, and show selectivity over sulphate, halides and acetate. The linear range of all these electrodes is approx. 10(-1)-10(-5) M with a near Nernstian slope and a reproducibility of 1%. The electrodes are stable and can be used continuously.     

Ion-selective electrodes based on silver sulphide

A series of electrodes with membranes of silver sulphide have been prepared. Their standard potentials and their response to sulphide and silver ions are measured and compared with those of a single-crystal silver sulphide electrode. The selectivity parameters against heavy metal ions and halides, as well as cyanide, are discussed. It is concluded that only interferences from cyanide ions and mercury(II) ions are detrimental to the practical use of the electrodes for measuring pAg and pS.     

Ion-selective electrodes – istory and conclusions

 The working mechanism of ion-selective electrodes has been investigated. The contradictions of theories deduced from so-called analogous phenomena are discussed in detail. Based on experiments made by the author’s research group the conclusion was drawn that only the surface (the active groups located there) takes part in the potential-determining reaction and the bulk resistance of the membrane plays a role only in the selection of the instrument used for potential measurement. Received: 15 May 1995/Revised: 12 August 1995/Accepted: 11 August 1995     

Ion-selective electrodes under galvanostatic polarization conditions

The application of ion-selective electrodes (ISE) with ionophore-based membranes under galvanostatic polarization conditions is briefly reviewed. The possibilities offered by polarization for expanding the working range of ISE and for varying their selectivity and the type of electrode response (cationic or anionic) are discussed.     

Ion-selective electrodes – istory and conclusions

 The working mechanism of ion-selective electrodes has been investigated. The contradictions of theories deduced from so-called analogous phenomena are discussed in detail. Based on experiments made by the author’s research group the conclusion was drawn that only the surface (the active groups located there) takes part in the potential-determining reaction and the bulk resistance of the membrane plays a role only in the selection of the instrument used for potential measurement. Received: 15 May 1995/Revised: 12 August 1995/Accepted: 11 August 1995     

Ion-selective electrodes for gold and silver determination

Some new ion-selective electrodes for silver and gold are described. They are based on the ion-associate species formed by the cyanide, chloride or thiourea complexes of the metals, with hydrophobic anions or cations, as appropriate. The electrodes have been applied to the determination of gold and silver in various technological process solutions in industry.     

Ion-selective electrodes with sensitivity in strongly diluted solutions

The present-day views on the nature of the lower detection limit of ion-selective electrodes with ionophore-based solvent polymeric membranes are discussed. The advantages and the disadvantages of various known approaches aimed at large improvement of the lower detection limit of these electrodes are scrutinized.     

Ion-selective electrodes in organic functional group analysis: Microdetermination of the amino group using the chloride electrode

Ohne Zusammenfassung

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Limits of detection of the six structural-isomeric xylenols (dimethyl phenols) on ready-made foils UV 254 and silica gel G with different spraying reagents

     

Ion-selective chalcogenide electrodes for a number of cations

Ion-selective chalcogenide disc electrodes have been developed which are responsive to cations such as silver, lead, chromium(III), nickel, cobalt(II), cadmium, zinc, copper(II) and manganese(II) ions. Each was prepared by using the corresponding metal chalcogenide with silver sulphide. An electrode was assembled with both a compacted and a sintered disc. The sintered electrodes were more sensitive and stable than the compacted ones. Response to silver ion was 59.5 mV pAg , to lead, nickel, cadmium, zinc and copper(II) 29.5 mV pM and to chromium(III) 20 mV pM . Cobalt(II) and manganese(II) electrodes had a non-Nernstian response of 25 mV pM . Both selenides and tellurides can be used for potentiometric determination, but the manganese(II) electrode serves as an analytical tool only when the disc consists of manganese(II) telluride and silver sulphide.     

Ion-selective electrodes in organic functional group analysis: Micro- and submicro-determination of thiocarbonyl and thiol groups using the silver/sulphide and iodide electrodes

Summary Thiocarbonyl and thiol groups in organic compounds are determined by reaction with 1N iodine in carbon tetrachloride in the presence of pyridine, whereby 4 equivalents and 1 equivalent of iodide ion are quantitatively released per group, respectively. The iodide ions in an aqueous extract are potentiometrically titrated with silver nitrate using the solid-state silver/sulphide selective electrode. The results obtained with samples down to 70g show an average recovery of 98.6% and no interferences are caused by unsaturated functions. Measurement of the iodide ion using the iodide ion-selective electrode and the known addition technique gives results with an absolute error of 2%.

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Zusammenfassung Thiocarbonyl- und Thiolgruppen in organischen Verbindungen werden mit Hilfe der Reaktion mit 1-n Jod in Tetrachlorkohlenstoff in Gegenwart von Pyridin bestimmt, wobei 4 bzw. 1 Jodidäquivalente gebildet werden. Diese werden in wäßriger Phase potentiometrisch mit Silbernitrat unter Verwendung der selektiven Silber/Sulfid-Elektrode titriert. Die Ergebnisse bei Einwaagen bis herunter zu 70g betragen durchschnittlich 98,6%. Ungesättigte Gruppen stören nicht. Die Bestimmung der Jodidionen mit jodidselektiver Elektrode unter Anwendung der bekannten Zugabetechnik führt zu Ergebnissen mit einem absoluten Fehler von 2%.

     

Ion-selective electrodes based on molecular tweezer-type neutral carriers

Potentiometric properties of cholic and deoxycholic acid derivatives substituted with various ion-recognizing moieties, such as dithiocarbamate, bipyridyl, glycolic and malonic diamides, urea and thiourea, and trifluoroacetophenons (TFAP), have been studied using solvent polymeric membranes. The dithiocarbamate and bipyridyl group containing ionophores exhibit high silver ion selectivity. The cholic acid derivatized with glycolic diamides exhibited high calcium selectivity, but its complex formulation constant was 10⁵ times smaller than that of ETH 1001. The reduced calcium binding ability of the glycolic diamide-substituted ionophore was advantageous for eliminating anionic interference. The bi- or tripodal malonic diamide-substituted ionophores exhibited substantially increased magnesium selectivity. Anion-selective ionophores have been designed by substituting urea and thiourea group containing chains to the hydroxyl linkers of chenodeoxycholic acid frames; their selectivity closely followed the sequence of Hoffmeister series, except the unusually large response of the thiourea-substituted ionophore to sulfate. The most successful examples of cholic or deoxycholic acid frame-based ionophores are those functionalized with two carbonate-selective TFAP groups: bipodal TFAP groups behaves like a tweezers for the incoming carbonate, and exhibit analytically interference free and quantitative responses to the carbonate in serum and seawater samples.