Rapid determination of telmisartan in pharmaceuticals and serum by the parallel catalytic hydrogen wave method

The polarographic characteristics of telmisartan have been investigated in 0.8 mol L^–1 NH₃.H₂O–NH₄Cl (pH 8.9)–0.01 mol L^–1 H₂O₂ as supporting electrolyte. The results demonstrate that the polarographic reduction wave at ca. –1.30 V in the absence of H₂O₂ is a catalytic hydrogen wave, and the reduction wave enhanced by H₂O₂ is a so-called parallel catalytic hydrogen wave. The analytical sensitivity of the parallel catalytic hydrogen wave is ca. 60 times higher than that of the corresponding catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave a novel method has been developed for determination of telmisartan by linear sweep polarography. The calibration curve is linear in the range 2.0×10^–8–2.0×10^–6 mol L^–1 and the detection limit is 1.0×10^–8 mol L^–1. The precision is excellent with relative standard deviations of 2.6% at a concentration of 1.0×10^–7 mol L^–1 telmisartan. The proposed method has been applied to the direct determination of the telmisartan in capsule forms and biological samples. The proposed method has been proved to be advantageous over existing CZE and MEKC methods in simplicity, rapidity, and reproducibility.     

Direct determination of iron in ferritin using the polarographic catalytic current

A new method for the determination of iron in ferritin using the polarographic catalytic current has been developed. Iron is released in NaOH and triethanolamine (TEA) solution and subsequently determined based on the polarographic catalytic wave in the presence of bromate with the peak potential of –1.0 V (vs.SCE). The 2.5-derivative peak height of iron is linearly proportional to its concentration in the range of 8.0 × 10^–8–1.0 × 10^–6 g/ml with a correlation coefficient of 0.9991. The method has been applied to the determination of iron in human fetal liver and horse-spleen ferritin and the recovery is 95–112%.     

Polarographic behaviour and determination of beclomethasone dipropionate

The polarographic behaviour of beclomethasone dipropionate in Britton-Robinson buffers containing 40% methanol as a solubilizer has been studied. Over the pH range 1.8–12, a cathodic wave was produced, which was characterised as being irreversible, diffusion controlled and free from adsorption phenomena. The number of electrons involved in the reduction was found through comparative study with spironolactone. Using direct current polarographic mode, the limiting current concentration plot is rectilinear over the range 2.5 × 10^–5 to 4 × 10^–4 mol/1 with a detection limit of 2.5 × 10^–6 mol/1. A method has been developed for the determination of the drug in aerosols and creams, the results being in agreement with those obtained by the official method.     

Untersuchungen zum polarographischen Verhalten des Rheniums in perchlorsauren L?sungen

Zusammenfassung Das polarographische Verhalten des Rheniums(VII) wurde in konzentrierteren PerchlorsäureLösungen untersucht. Zur Bestimmung kleiner Rhenium(VII)-Konzentrationen ist eine 10 M Perchlorsäure geeignet. Die Bestimmung kann mit der Gleichstrom-, Wechselstrom- und differentiellen Pulse-Polarographie durchgeführt werden. Mit der Gleichstrompolarographie lassen sich noch 2·10^–8 M Re(VII) erfassen. Die Eichkurven sind im Bereich von 5·10^–8 bis 6·10^–5M linear. Die Temperatur- und Tropfzeitabhängigkeit der polarographischen Ströme macht ihren katalytisch/kinetischen Ursprung wahrscheinlich.

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Investigations on the polarographic behaviour of rhenium in perchloric acid solutions

Summary The polarographic behaviour of rhenium(VII) was investigated in perchloric acid solutions of higher concentrations. For the polarographic determination of small concentrations of rhenium(VII) a 10 M perchloric acid is properly suited. The determination can be performed by DC-, AC- and DP-polarography. With DC-polarography 2×10^–8 M Re(VII) can be detected. The calibration curves are linear in the range from 5×10^–8 to 6×10^–5M Re(VII). From investigations of the temperature- and droptime dependence the catalytic/kinetic origin of the polarographic currents is made probable.

     

Die kinetische polarographische Stufe des Urans in Gegenwart von Chlorat-Ionen

An increase of the 2nd polarographic uranium(VI) wave has been observed in the presence of chlorate ions in HClO₄–NaClO₄, or HClO₄–NaClO₄–NaCl supporting electrolyte, resp. The polarographic measurements at different temperatures and at various perchloric acid concentrations show that this increase is due to a kinetic U(III)-U(IV) current. The activation parameters of the U(III)-U(IV) oxidation reaction with ClO₃ ^– have been calculated usingKautecky's method.The approximately 5fold increase of the 2nd polarographic wave allows the determination of small amounts of uranium (10^–5–10^–6 mole/l).

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Mit 2 Abbildungen     

氢醌对胆红素氧化过程的促进作用及其分析意义

研究了氢醌与胆红素的作用过程，发现氢醌在碱性条件下可促使胆红素氧化，且胆红素被氧化成胆绿素，此反应过程被证实为自由基反应，考察了介质条件，抗氧化剂等反应过程的影响及其它酚类物质对胆红素氧化的作用情况。     

Polarographic behaviour of 2-benzilidenimino-benzohydroxamic acid (2-BIBH) and 2-BIBH-Mo(VI) system

The polarographic behaviour of 2-benzilideniminobenzohydroxamic acid (2-BIBH) solutions and of 2-BIBH solutions in the presence of Mo(VI) have been studied by using differential pulse polarography and cyclic voltammetry. The polarographic characteristics of the resulting waves have been studied and possible mechanisms of the processes involved have been proposed. A linear relationship has been observed betweenI _p and Mo(VI) concentration in the range 2×10^–6 to 1.6×10^–5 M when using 3×10^–4 M 2-BIBH. Standard deviations of 5.6×10^–8 and 1.2×10^–8 M were found for 3×10^–6 and 8 × 10^–6 M Mo(VI), respectively.     

Polarographic study of a benzodiazepinooxazole: Oxazolam

Summary The polarographic behaviour of 10-chloro-2,3, 7,11b-tetrahydro-2-methyl-11b-phenyloxazolo-[3,2-d][1,4]-benzodiazepin-6(5H)-one (Oxazolam) was studied in the pH range 1–12. The reduction processes of Oxazolam and its hydrolysis product are irreversible and their currents are predominantly diffusion-controlled. The linear relationship between current and Oxazolam concentration in sulphuric acid medium permits its polarographic determination up to 6.08×10^–5 mol/l. The detection limit was 1.52×10^–7 mol/l (50 ppb). The reproducibility of the method in terms of relative standard deviation was 1.74% and 1.85% for ten determinations at 1.48×10^–5 mol/l and 1.37×10^–6 mol/l levels, respectively. The method developed was applied to the determination of the compound in its formulations, Hializan-10 mg, obtaining errors lower than 2%.

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Polarographische Untersuchung eines Benzodiazepinoxazols: Oxazolam

     

Polarographic study of a benzodiazepinooxazole: Cloxazolam

Summary The polarographic behaviour of 10-chloro-11b-(2-chlorophenyl)-2,3,7,11b-tetrahydrooxazolo[3,2-d][1,4]-benzodiazipine-6(5H)-one (cloxazolam) was studied in the pH range 1–12. Cloxazolam suffers a hydrolysis process, which can be followed by polarography. The reduction processes of cloxazolam and its hydrolysis product are irreversible and their currents are diffusion-controlled. Two polarographic methods have been developed upon the basis of the reduction of both the protonated iminium form (pH 1.45, measurement time: 10 min) and the benzophenone produced in the hydrolysis process (pH 11.75, measurement time: 15 min). The relationship between reduction peak current and concentration is linear up to at least 5.72×10^–5 mol/l for both methods. A higher sensitivity was obtained for the method based on the benzophenone reduction (detection limit 5.72×10^–8 mol/l; 20 ppb). The methods developed were applied to the determination of cloxazolam in its pharmaceutical formulations (Betavel, 1 mg). The method in alkaline medium was the most adequate for the determination of the compound in tablets, with errors lower than 1%.

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Polarographische Untersuchung eines Benzodiazepinoxazols: Cloxazolam

     

Determination of methylviologen (Paraquat) by differential pulse polarography

Summary Determination of Methylviologen (Paraquat) by Differential Pulse Polarography The second reduction wave of methylviologen (Paraquat) has been studied at pH 2 by different polarographic techniques. The limiting current is diffusion-controlled. Evidence for dimerization of the radical formed in the first reduction step has been obtained. The n values for the reduction process have been calculated at concentration levels where the dimer and the monomer predominate. Paraquat can be determined by differential pulse polarography in the 6.0×10^–5–4.0×10^–7 M concentration range, the limit of determination being 1.7×10^–7 M. The method has been applied to paraquat determination in commercial herbicides.     

Polarographic and voltammetric determination of trace amounts of 2-nitronaphthalene

The polarographic behaviour of 2-nitronaphthalene was investigated by DC tast polarography (DCTP) and differential pulse polarography (DPP), both at a dropping mercury electrode, and differential pulse voltammetry and adsorptive stripping voltammetry, both at a hanging mercury drop electrode. Optimum conditions have been found for the determination of 2-nitronaphthalene by the given methods in the concentration ranges of 2×10^–6–1×10^–4, 2×10^–7–1×10^–4, 1×10^–8–1×10^–4 and 2×10^–9–1×10^–8 M, respectively. Practical applicability of these techniques was demonstrated by the determination of 2-nitronaphthalene in drinking and river water after its preliminary separation and preconcentration using liquid–liquid and solid-phase extraction with limits of determination of 3×10^–10 M (drinking water) and 3×10^–9 M (river water).     

Polarographic studies on some arylarsonic acids

Summary The polarographic behaviour of a series of substituted phenylarsonic acids over the concentration range 5×10^–5M–10^–3M and pH range 0–3 was studied and a mechanism for the polarographic reduction proposed, taking into account the results of various analyses performed on the products of macro-scale electrolytic reductions. A method for the analysis of phenylarsonic acids utilising the reduction wave is also presented.

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Polarographische Untersuchungen einiger Arylarsonsäuren

Zusammenfassung Das polarographische Verhalten einer Reihe von substituierten Phenylarsonsäuren wurde im Konzentrationsbereich 5 · 10^–5M–10^–3M bei pH 0–3 untersucht und ein Mechanismus für die polarographische Reduktion aufgestellt, der auch die Ergebnisse von elektrolytischen Reduktionen im Makrobereich berücksichtigt. Eine Methode für die Analyse von Phenylarsonsäuren, mit Hilfe der polarographischen Reduktionsstufe wird beschrieben.

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Research Institute for Technical Physics of the Hungarian Academy of Sciences, Budapest IV.     

Electrolyses of organic compounds with microelectrodes with renewable surfaces: Comparison of dropping mercury and mercury pool electrodes

Controlled potential electrolysis with a dropping mercury electrode (DME), which is a microelectrode with a periodically renewed surface, is usually carried out in small volumes (0.5–1.0 ml) of diluted solutions (10⁻³–10⁻⁴M). Such electrolysis can be used for identification of products and determination of their yields in the elucidation of mechanisms of polarographic reduction of organic compounds. Controlled potential electrolysis with a mercury pool electrode, which is a large-scale electrode with a surface that is not renewed, is usually used in coulometry and preparative electrolysis of larger volumes (10–100 ml) of more concentrated (10⁻²–10⁻³M) solutions, when the goal is preparation of a larger amount of electrolysis product. Identification of products and determination of yields when the DME is used involves microchemical techniques. Frequently, information obtained by the DME and Hg pool electrolysis is similar. In some instances the nature of products formed, the number of electrons transferred, and the shape of current-voltage curves obtained by the micro- and macroelectrodes differ. Such differences can involve a number of waves, their potentials, the ratio of wave heights, and shapes of the waves. These dissimilarities can be caused by differences in time scale, reaction conditions, adsorption and other interactions at the electrode surface, concentration, and pH control. Concentration changes of starting material, intermediates, and products in the course of electrolysis can be followed spectrophotometrically or using polarographic current-voltage curves. Time dependence of current-voltage curves in the course of electrolysis can indicate the role of chemical reactions accompanying the electrolysis. Comparison of current-voltage curves and the nature of electrolysis products obtained with micro- and macroelectrodes can contribute to a better understanding of electrode processes and to development of better analytical methods.     

Polarographic studies on the N-benzoylphenylhydroxylamine complex of tin and pulse polarographic determination of trace quantities of tin after extraction

Summary A polarographic investigation on the N-benzoylphenylhydroxylamine (BPHA) complex of tin has been made in a mixture of chloroform and methanol. From the studies it has been confirmed that the complex is formed by tetravalent tin. A tentative mechanism of the oxidation of tin(II) in presence of BPHA has been suggested. Moreover, a rapid, sensitive and specific method of determination of tin in trace quantities by derivative pulse polarography has been developed. The chloroform extract can be directly subjected to polarography after addition of requisite quantities of water and methanolic lithium perchlorate. Effect of different supporting electrolytes on the system has been studied. By the described method 7×10^–7 M to 2×10^–5 M tin can be determined without interference from large quantities of the elements commonly associated with tin and also from a large number of other elements and complexing agents.

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Polarographische Untersuchung des N-Benzoylphenylhydroxylamin-Komplexes mit Zinn und pulspolarographische Bestimmung von Zinn im Spurenbereich nach Extraktion

Zusammenfassung Eine polarographische Untersuchung des N-Benzoyl-phenylhydroxylamin (BPHA)-Komplexes mit Zinn in einer Mischung von Chloroform und Methanol wurde durchgeführt. Es konnte festgestellt werden, daß der Komplex von vierwertigem Zinn gebildet wird. Ein Mechanismus der Oxidation von Zinn(II) in Gegenwart von BPHA wird vorgeschlagen. Die entwickelte Methode eignet sich in Verbindung mit der derivativen Pulspolarographie zur schnellen, spezifischen und empfindlichen Bestimmung von Zinn im Spurenbereich. Nach Zugabe einer bestimmten Menge Wasser und methanolischer Lithiumperchloratlösung kann der Chloroform-Extrakt des Zinn-BPHA-Komplexes direkt polarographiert werden. Der Einfluß verschiedener Leitsalze wurde untersucht. Mit diesem Verfahren läßt sich Zinn im Bereich von 7×10^–7 M bis 2×10^–5 M in Anwesenheit großer Mengen anderer Metallionen und Komplexierungsmittel bestimmen.

     

Polarographic behaviour of n-butyl thioglycolate

The polarographic behaviour of n-butyl thioglycolate, [HSCH₂OOC(C₄H₉)] has been studied in 25% ethanol, 0.1M-KNO₃ and 0.002% Triton X-100 in the pH range 1.96–11.84 at the d.m.e. The polarograms consist of two waves, a pre-wave of constant height followed by a normal anodic wave. The electrode reaction is reversible and diffusion controlled involving one electron transfer process. The maximum number of moles adsorbed per unit area is 1.30×10^–9 mole/cm², i.e. 7.82×10¹⁴ molecules/cm², which corresponds to an area 12.84 Å per adsorbed molecule. The adsorption coefficient and molar adsorption energy have been calculated to be 43.4×10⁴ and 142.8 kcal/mole respectively. The dissociation constant (pK) of the sulphydryl group is found to be 9.4.With 1 Figure     

Some electroanalytical aspects of using pulse polarography for determination of Ge(IV)

Summary Presented data give some informations of analytical importance as a result of pulse polarographic investigations of Ge(IV) in KCl solutions within pH range 3–12 at Ge concentration from 1×10^–4 to 2.5×10^–6 M. It was shown that Ge(IV) can be polarographically active in acidic solution but its reduction interferes with hydrogen gas development. The addition ofp-quinone enables the determination of Ge(IV) without this interfering effect.Suggested explanation of the observed changes in polarographic curves dependent on pH and Ge concentration based on the existence of several polarographically active forms.

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Elektroanalytische Bemerkungen zur pulspolarographischen Bestimmung von Ge(IV)

Zusammenfassung Unsere Ergebnisse bieten einige Informationen über die pulspolarographische Bestimmung von Ge(IV) in KCl-Lösungen innerhalb pH 3–12 und bei Ge-Konzentrationen zwischen 10^–4 und 2,5×10^–6 M. Es wurde gezeigt, daß Ge(IV) in saurer Lösung polarographisch aktiv ist, seine Reduktion aber durch Wasserstoff-Entwicklung gestört wird. Der Zusatz vonp-Chinon beseitigt diese Störung. Die Änderung der polarographischen Kurven je nach Ge-Konzentration und pH beruht vermutlich auf der Existenz verschiedener polarographisch aktiver Formen.

     

Polarographic behaviour and determination of paracetamol and salicylamide after treatment with nitrous acid

A polarographic procedure is described for the determination of paracetamol (acetaminophen) and salicylamide after treatment with nitrous acid. The different experimental parameters affecting the derivatization process and the polarographic analysis were studied. The derivatization products were found to be reduced at the dropping mercury electrode over the whole pH range in Britton-Robinson buffers. At pH 7.0, well defined diffusion-controlled cathodic waves were produced for both compounds. Plots of limiting current vs. concentration were linear over the ranges 0.05–0.75 and 0.25–1.5mM for paracetamol and salicylamide, respectively, in the d.c. mode, with minimum detectability of 2.5 × 10^–6 and 1.25 × 10^–5 M, respectively. The procedure was applied to the analysis of some pharmaceutical dosage forms and the results were in good agreement with those obtained by official and compendial methods.     

Determination of acipimox in capsules by differential pulse polarography

A differential pulse polarographic (DPP) method has been developed for the determination of acipimox in its pharmaceutical formulations. Using Sörensen buffer pH 6.0 as supporting electrolyte a single, irreversible peak occurred at –0.79 V vs an Ag/AgCl reference electrode. The peak height vs concentration plot was found to be linear over the range of 10^–6 to 6 × 10^–4 mol/l. The detection limit is 60ng/ml. The analysis of a series of 10 Olbetam® 250 mg capsules showed an overall standard deviation of ± 4.18 mg and a S_rel of ± 1.66%, respectively.     

Kathodenstrahlpolarographische Bestimmung von Spurenelementen in Zinnchloriden

Zusammenfassung Eine Methode wird beschrieben, die die kathodenstrahlpolarographische Bestimmung von Spuren Ni, Pb, Mn, Co, Cu, Fe, Mo in Zinnchloriden in den Bereichen 10^–4% (Ni, Pb, Mn, Cu, Fe) und 10^–5% (Mo, Co) gestattet. Über den stark basischen Anionenaustauscher AG 1×8 wird das Zinn von den Spurenelementen getrennt.

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Cathode-ray polarographic determination of trace elements in tin chlorides

A method is described for the cathode-ray polarographic detemination of traces of Ni, Pb, Mn, Co, Cu, Fe, and Mo in tin chlorides. Tin is separated from the trace metals by ion exchange on the strong basic anion-exchange resin AG 1×8. The detection limits are within the ranges of 10^–4% and 10^–5%.

     

Investigations on the redox character of dithizone by voltammetric methods : Part I.The reduction of dithizone in aqueous solutions

The mechanism of the electrochemical reduction of dithizone to the corresponding hydrazo compound, diphenylthiocarbazide, has been examined in detail by polarographic and voltammetric techniques over a wide pH range. The reaction is reversible and dithizone can be determined polarographically in the range 10^-3–10^-5M. This polarographic behaviour suggests new applications of dithizone as an electroanalytical reagent.