Determination of some monoazo compounds by derivative pulse polarography

Summary The determination of some monoazo compounds by derivative pulse polarography has been investigated. The effect of pH is studied, and the optimum pH was determined to give the highest sensitivity. The detection limit is ca. 1×10^–5 M. Response is linear up to 8×10^–4 M.

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Bestimmung einiger Monoazoverbindungen durch derivative Pulspolarographie

Zusammenfassung Die Bestimmungsmöglichkeiten für einige Monoazoverbindungen durch derivative Pulspolarographie wurden untersucht. Der Einfluß des pH-Wertes wurde getestet und der jeweils optimale Wert in Abhängigkeit von den Substituenten ermittelt. Die Nachweisgrenze liegt bei 1×10^–5 M. Die Anzeige ist linear bis 8×10^–4 M.

     

Metallchelate mit Acetophenon-Benzoylhydrazon und Acetophenon-Salicoylhydrazon

The stoichiometry and structure of acetophenone benzoylhydrazone and acetophenone salicoylhydrazone chelates with some divalent metal ions are studied by conductometric titration and visible and infra-red absorption spectrophotometry. The results are supported by analysis of the solid complexes. The infra-red study revealed that coordination occurs through C=O and C=N groups. The shift in the C=O and C=N bands is utilised for the determination of bond lengths.     

Comparative studies on the adsorption and association of 3-methylxanthine and 7-methylxanthine at a charged interface

Summary A systematic comparative study of the adsorption and association of 3-methylxanthine (3MXan) and 7-methylxanthine (7MXan) at mercury-solution interfaces in acidic, neutral, and alkaline buffer solutions was undertaken by ac voltammetry. At bulk concentrations of3MXan above a threshold value, the stacking interactions between vertically oriented molecules lead to a slow reorientation aroundE _ecm, and the molecules adopt a perpendicular orientation. The association of the adsorbed molecules of7MXan is hindered and is not effective in promoting base-base stacking interactions. The enhanced surface activity of3MXan compared to7MXan results from the different position of the methyl group in the purine moiety. The effect of some divalent metal ions on adsorption stages and association of the investigated compounds has been studied. The results indicate that the complexation of methylated xanthine enhances the stacking interactions and hence would be expected to facilitate the formation of perpendicularly stacked layers ofM(II)-MXan complexes on the electrode surface. The adsorption parameters of the investigated compounds have been computed in absence and presence of Cu(II) at differentpH values. The results are compared with the behaviour of xanthine.

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Vergleichende Untersuchungen zur Adsorption und Assoziation von 3-Methylxanthin und 7-Methylxanthin an einer geladenen Grenzfläche

Zusammenfassung Eine systematische vergleichende Untersuchung zur Adsorption und Assoziation von 3-Methylxanthin (3MXan) und 7-Methylxanthin (7MXan) an Quecksilber-Lösungs-Grenzflächen wurde mittels AC-Voltammetrie in sauren, neutralen und basischen Pufferlösungen durchgeführt. Oberhalb einer bestimmten Grenzkonzentration kommt es durch Wechselwirkungen zwischen vertikal angeordneten3MXan-Molekülen zu einer langsamen Reorientierung umE _ecm, was zu einer senkrechten Anordnung führt. Die Assoziation von7MXan ist gehindert und erlaubt daher keine ausgeprägten Basen-Basen-Wechselwirkungen. Die erhöhte Oberflächenaktivität von3MXan gegenüber7MXan resultiert aus der unterschiedlichen Stellung der Methylgruppe am Purinrest. Der Effekt einiger zweiwertiger Metallionen auf die Adsorption und Assoziation von3MXan und7MXan wurde untersucht. Die Ergebnisse weisen auf eine Begünstigung der Wechselwirkungen hin; die Bildung von vertikal angeordneten Grenzschichten an der Elektrodenoberfläche sollte daher im Fall vonM(II)-Mxan-Komplexen erleichtert sein. Die Adsorptionsparameter der untersuchten Verbindungen wurden in Abwesenheit und in Gegenwart von Cu(II) bei verschiedenenpH-Werten berechnet. Die Ergebnisse werden mit dem Verhalten von Xanthin verglichen.

     

Application of differential pulse polarography for trace determination of polycytidylic acid in absence and presence of some metal ions

Summary A differential pulse polarographic method has been applied to the determination of trace concentrations of polycytidylic acid (Poly-C) in absence and presence of metal ions. The applicability of differential pulse polarography for the trace determination of the investigated biological compound was examined with regard to the dependence of differential pulse current on various parameters such as pH, pulse amplitude, scan rate and drop time. The selectivity of this technique for the determination of binary and a ternary mixtures of poly-C and some metal ions has been also reported. Limits of detection and quantitation have been calculated for the differential pulse polarographic determination of the poly-C and various metal ions. The validity of this method is supported by the constancy of the i_p/C values and a statistical analysis is included on calibration curve parameters and observed concentration.     

Voltammetric and spectroscopic studies on binding of antitumor Morin, Morin-Cu complex and Morin-beta-cyclodextrin with DNA

A systematic comparative study of the binding of antitumor Morin and its complexes with DNA has been investigated in the Britton-Robison (BR) buffer solutions using voltammetric and spectroscopic methods. The results show that Morin molecule, acting as an intercalator, is inserted into the cavity of the beta-cyclodextrin (beta-CD) as well as into the base stacking domain of the DNA double helix. The interaction of Morin-Cu complex or the inclusion complex of Morin-beta-CD with ds-DNA causes hypochromism in the absorption spectra, along with pronounced changes in the electrochemical behavior of the Morin complexes. An isobestic point and a new spectrum band appeared indicating the formation of the new system of Morin-Cu-DNA at lambda(m)=391 nm and Morin-beta-CD-DNA at lambda(m)=375 nm. The intercalation of Morin-Cu and Morin-beta-CD complexes with DNA produces an electrochemically inactive supramolecular complex. The binding constants were calculated from the increase of the solubility, the strong hypochromism, and the decrease in peak current of Morin and its complexes upon the addition of the host molecules. Calculation of the thermodynamic parameters of the interaction of the inclusion complex of Morin-beta-CD with DNA, including Gibbs free energy change, Helmholz free energy and entropy change shows that the complexation is a spontaneous process of association.     

Studies on the reaction of salicylidenebenzoic-hydrazide (SBH) with Ce3+, Th4+ and UO2 2+

The stoichiometry and structure of salicylidenebenzoic-hydrazine (SBH) chelates with UO₂(II), Ce(III) and Th(IV) in buffer-ethanol mixtures and in pure ethanol is studied applying conductometric titration, visible spectrophotometry and ir-spectrophotometry. The ir-spectra revealed that coordination takes place through the C=O and C=N groups.Deceased December 1977.     

Cathodic Adsorptive Stripping Voltammetric Determination of the Antitumor Drug Rutin in Pharmaceuticals, Human Urine, and Blood Serum

Cathodic adsorptive stripping voltammetry (CASV) was applied for the determination of rutin in pharmaceuticals, human urine, and blood serum. An electrochemical stripping procedure for trace measurements of rutin was developed based on the adsorption of the Cu²⁺-rutin complex on a hanging mercury drop electrode and applied to the quantification of the drug. Cyclic voltammetry was used to characterize the interfacial and redox behavior of the adsorbed Cu²⁺-rutin complex. Experimental and instrumental parameters for quantitative determination were optimized, and a detection limit of 4.9 × 10⁻⁹ mol · L⁻¹ in presence of Cu²⁺-ions for quantification of rutin under optimum conditions was derived. The sharp peak of the adsorbed Cu²⁺-rutin complex associated with an effective interfacial accumulation of this compound facilitates the determination of rutin in biological fluids with good recoveries. The degree of interference from potentially present metal ions and organic compounds on the CASV signal for Cu²⁺-rutin complex was evaluated.     

Differential pulse polarographic determination of poly(8-hydroxyquinoline) in the presence and absence of an insulating poly(vinyl alcohol) matrix

The electrochemical activity of poly(8-hydroxyquinoline) (PHQ) in acid and alkaline media has been investigated by use of differential pulse polarography (DPP). The reduction peak height (I(p)) of PHQ in universal buffer solutions is not useful as an analytical signal, because it is highly affected by hydrogen evolution in acid media and appears as a small peak located at more negative potential values in alkaline media. A new and highly sensitive reduction peak (E(p)=-0.45, pH 9.25) appears, however, after addition of trace amounts of PHQ to Cu(II), or vice versa. This reduction peak is a result of the reduction of Cu(II) chelates in the PHQ-Cu(II) complex and is highly promising for the trace determination of PHQ at nanomolar and submicromolar levels. The response current (I(p)/mu A) for the reduction peak of Cu(II) chelates in a PHQ-Cu(II) matrix results in sensitivity to the concentration of PHQ at least three orders of magnitude higher than that for the reduction peak of PHQ alone under the same conditions. The limit of detection is as low as 5.264 ppb (microg L(-1)). The effect of a variety of anions and cations and of an insulating poly(vinyl alcohol) (PVA) matrix has been investigated. Electroactive PHQ-Cu(II) at a level of 0.685% could induce a current of approximately 240 nA in an insulating PVA matrix, suggesting possible application for the preparation of a PHQ-Cu(II)-PVA electroactive composite.