A new micro-cell for continuous-flow pulsed voltammetric analysis

The effect of p-toluenesulfonate and trifluoromethanesulfonate supporting electrolytes on the polarographic reduction of some alkaline earth and transition metal ions in N,N-dimethylformamide and acetonitrile has been investigated. Trifluoromethanesulfonate behaved similarly to perchlorate in dimethylformamide, while the half-wave potentials in p-toluenesulfonate supporting electrolyte shift to more negative potentials than those in perchlorate. in acetonitrile, the half-wave potentials shift to more negative potentials in trifluoromethanesulfonate than in perchlorate. The effect of the supporting electrolyte on the shift of the half-wave potential can be explained as the ion-pair formation between the divalent cation to be reduced and the supporting electrolyte anion.     

Polarographic determination of nitrate in concentrated sulphuric acid solutions

The possibility of the polarographic determination of nitrates in the presence of hydroquinone in 65–95% sulphuric acid solutions was investigated. It has been found that nitrates in 95% acid have one polarographic wave without inflection point the height of which is proportional to nitrate concentration. In 85% sulphuric acid and in other acids investigated with lower concentrations, nitrates are not polarographically active. If both nitrate and hydroquinone are present in H₂SO₄, two waves are observed on the polarogram. The more negative wave is completely defined. The height of this wave is proportional to nitrate concentration in the range 5×10^?5?5×10^?3M.     

Differential pulse polarographic behaviors of p-nitrosodimethylaniline: Application for microdetermination of NADH

The differential pulse polarographic behavior of p-nitrosodimethylaniline has been investigated in Britton-Robinson buffer and phosphate buffer. The peak obtained at pH 8.0 is recommended for the trace determination of this compound, with an experimental detection limit of 18 ppb (1.2 × 10^?7M) in simple aqueous solution. The method is also applied for the indirect microdetermination of NADH. The experimental detection limit of NADH is shown to be 1.05 × 10^?6M.     

Polarographic Studies of Dithiodiacetic Acid and the Uranyl-Dithiodiacetic Acid Complex

The polarographic behaviour of dithiodiacetic acid and that of U(VI) in a solution containing dithiodiacetic acid as complexing agent have been investigated. For the dithiodiacetic acid system, two waves appear over the pH range studied. The prewave is kinetic in nature and the mainwave is diffusion-controlled. However, as U(VI) is added into the dithiodiacetic acid system, the polarogram changes due to the existence of a complex. The current-potential curve of the first wave is not the normal S shape. This is due to the superposition of the first wave of the ligand and the wave due to the reduction of the U(VI) in the complex to U(V). The second wave is due to the reduction of the complex The first wave is an adsorption-controlled current and the second wave is partly diffusion-controlled and partly adsorption-controlled. We propose an electrode reaction mechanism for both systems and the complex species. The dissociation constant of the complex HASSAUO⁺₂ is found to be of the order of 10^?4.     

Electroreduction and pulse-polarographic determination of nicotinamide in multivitamin tablets

The electroreduction of nicotinamide has been investigated by d.c., a.c. and pulse polarography, cyclic voltammetry and coulometry. A single well-defined polarographic wave is obtained from 2 M sulphuric acid and from 0.1 M sodium hydroxide. In both media, nicotinamide undergoes an irreversible 2-electron reduction; 3 hydrogen ions are consumed in acidic medium and two hydrogen ions in alkaline medium. The current is diffusion-controlled and proportional to the concentration in the range 0.6–120 μg ml^?1. Reduction mechanisms are proposed. A simple and rapid method for the determination of nicotinamide in multivitamin tablets by differential pulse polarography is described.     

Electrodimerization of the pyridiniumcarboxylic acids homarine and trigonelline

Homarine (1-methyl-2-carboxypyridinium ion) and trigonelline (1-methyl-3-carboxy-pyridinium ion) are reduced at mercury electrodes in alkaline solutions by a one-electron transfer to the pyridinium ring. Analysis of polarographic wave shapes using deviation-pattern recognition, peak widths of cyclic voltammograms, analysis of the products of bulk electrolyses and dependences of E_1/2 and E_p on scan rate, pH and concentration indicated that these reductions proceed by an EC² mechanism, where the second-order chemical reaction is a homogeneous dimerization. The zwitterionic form of the pyridiniumcarboxylic acid, which predominates in alkaline solutions, undergoes reduction to form a pyridinyl anion radical. Two radicals then couple to yield a dimer dianion which is subject to protonation. The dimer can be oxidized at mercury electrodes.     

Electroreduction and polarographic determination of nitrazepam in serum

The electroreduction of nitrazepam has been investigated by polarography, cyclic voltammetry, chronopotentiometry and controlled potential coulometry. The drug is decomposed in acidic and alkaline solutions but is fairly stable in neutral media. In phosphate buffer pH 6.9 the reduction occurs in two steps. The first step is a 4-electron reduction of the nitro group to the hydroxylamine and the second step is a 2-elcctron reduction of the azomethine (>C=N-) group. The first polarographic wave probably involves a rate-determining 2-electron reduction of the nitro group. This wave is well defined and suitable for determination of the drug in the range 10 ⁻⁶- 5·10⁻⁴M. The half-wave potential is -0.38 V vs. Ag/AgCl, and the current is diffusion-controlled. The oxidized form of nitrazepam is strongly adsorbed at the electrode surface, hence the drug can be determined in the presence of surface-active substances like proteins. A procedure has been developed for the direct polarographic determination of microgram quantities of the drug in serum. The proposed method is very rapid and accurate and permits determination of 0.5 -80 μg per ml of the drug in serum.     

Electrochemical studies of sulfonates in non-aqueous solvents: Part I. Polarographic reductions of alkali metal ions with sulfonate supporting electrolyte in N,N-dimethylformamide and acetonitrile

The effect of the supporting electrolytes tetraethylammonium p-toluenesulfonate, methanesulfonate and trifluoromethanesulfonate on the polarographic reduction of alkali metal ions in N,N-dimethylformamide and acetonitrile has been investigated. In tetraethylammonium trifluoromethanesulfonate supporting electrolyte, the polarographic reductions of alkali metal ions are almost the same as those in perchlorate in both solvents. In tetraethylammonium p-toluenesulfonate and methanesulfonate, the half-wave potentials shift to more negative potentials, especially in acetonitrile. These shifts can be explained in terms of ion-pair formation between the alkali metal ion and the supporting electrolyte anion.     

Investigation of Cu(II)/2′, 3′-Isopropylidene Adenosine Complex

Abstract

The UV spectrum and polarographic behavior of Cu(II)/IpA complex was investigated, in an aqueous solution of Cu(II)/IpA complex, in Britton Robinson buffer solution at a pH from 5.0 to 8.0. At a low concentration of Cu(II)/IpA complex, maximum absorbance was shown to be 532 nm.

Only one polarographic wave was found dependent on a two electron reduction.

The composition ratio of the complex was obtained by both UV spectrum and polarography, it was found that the ratio of Cu(II) to IpA was 1:2. The polarography vas shown by a two-electron reduction wave.     

The polarographic behaviour of the 1,4-benzodiazepines, oxazepam and lorazepam, and a method for quality control

The polarographic behaviour of the drugs, oxazepam and lorazepam, has been investigated over a wide pH range. Different types of wave are obtained depending on the pH. The pK_a, values calculated are in good agreement with those obtained from u.v. spectroscopic measurements. For analytical purposes, the optimal pH is 4.7 (acetate supporting electrolyte), the 4-electron reduction wave being measured. A quality control method for the two drugs in different formulations containing 0.5–15 mg of active constituent is described.     

A pulse polarographic investigation of parathion and some other nitro-containing pesticides

The polarographic behaviour of parathion, its major metabolites (paraoxon and p-nitrophenol), and of methylparathion, EPN and pentachloronitrobenzene has been studied over a wide pH range. Differential pulse polarography is used to differentiate between parathion, p-nitrophenol and pentachloronitrobenzene. An indirect determination of parathion in the presence of paraoxon can be based on their respective rates of hydrolysis in 0.5 M sodium hydroxide solution. The electrochemical behaviour of these compounds has also been investigated in solutions containing tetraalkylammonium salts as the supporting electrolyte.     

Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

A polarographic study of the complexes formed in alkaline solution by the cadmium(II) ion with ethylenediamine,N-(2-hydroxyethyl)ethylenediamine,and N,N′-bis(2-hydroxyethyl)ethylenediamine

A multiple regression analysis of polarographic data has been used to determine the formulas and formation constants of complexes formed in alkaline solution by reaction of cadmium(II) ion and hydroxide ion with ethylenediamine (en), N-(2-hydroxyethyl)-ethylenediamine (hn) and N,N′-bis(2-hydroxyethyl)ethylenediamine (2hn). The complexes formed are designated by the general formula Cd(A)_p(OH)_p^2?q and the formation constants are given as log β_pq. The complexes found and their formation constants are: for en, 1 : 2 (10.3), 1 : 3 (12.3), and 1 : 2 : 1 (12.2); for hn, 1 : 2 (9.5), 1 : 2 : 1 (12.2), and 1 : 2 : 2 (12.6); and for 2hn, 1 : 2 (8.9), 1 : 1 : 2 (11.1), 1 : 2 : 1 (11.2), and 1 : 2 : 2 (12.6). It is concluded that in each case for which the hydroxide ion is reacted, a proton is removed from an alcoholic hydroxyl group which is coordinated to form a five-membered chelate ring linking a nitrogen atom and oxygen atom to the cadmium(II) ion.     

The Polarographic Behaviour of Some Arylidene Benzoic Hydrazide Derivatives and Substituent Effect

The polarographic reduction of some arylidene derivatives of benzoic hydrazide are investigated at the DME. The polarograms in solutions of pH≤8 consist of a single wave corresponding to 4 electrons in acid media and 2 electrons in alkaline ones. The wave splite into two daughter waves in media of pH≥10, the more negative wave increases in height at the expense of ihe original one with rise of pH. The reduction waves are essentially diffusion controlled with one proton and two electrons in the rate determining step. The electrode reaction is discussed and the important kinetic parameters are determined.     

Efficient Protocol for Stereoselective Epoxidation of Cinnamic Esters Using TsNBr2

An efficient method has been developed for the synthesis of epoxide from cinnamic esters without any catalyst. The reaction was performed in CH₃CN–water (4:1) using N,N-dibromo-p-toluenesulfonamide (TsNBr₂) in alkaline conditions. This procedure can be utilized for stereoselective synthesis of epoxides from cinnamic esters in excellent yield in a shorter reaction time with exclusive formation of the trans-isomer. The method was further extended successfully for styrenes.     

The CuII−CuI−Cu0(Hg) system in the presence of benzotriazole: Part I. A polarographic investigation

A polarographic investigation of Cu^II electroreduction from solutions of benzotriazole (BTA) of pH from 1 to 3 at a dropping mercury electrode shows the presence of two successive adsorption waves of equal height (waves Ic and IIIc) due, respectively, to the formation and to the subsequent dissolution of an adsorbed film of a Cu^I compound. The dependence of the half-wave potential of wave IIIc, which is polarographically reversible, upon pH and BTA concentration indicates that the adsorbed film has the composition [Cu^I(BTA^?)], where BTA^? denotes the deprotonated anionic form of benzotriazole. Moreover, the maximum height of wave IIIc indicates that this film is one monolayer thick. A third cathodic wave (wave IIc), lying between waves Ic and IIIc, stems from the reduction to the metal state of the Cu^II ions diffusing from the bulk solution. Copper(0) oxidation at dropping amalgam electrodes in BTA solutions yields two successive adsorption waves (waves Ia and IIa). Wave Ia is due to the same electrode process, Cu⁰ (Hg)+BTA?Cu^I(BTA^?)+H⁺+e, responsible for the cathodic wave IIIc. On the other hand, wave IIa is due to the formation of roughly two adsorbed monolayers of [Cu^I(BTA^?)] upon that formed along wave Ia.     

The riboflavin—dihydroriboflavin system in acidic medium on mercury: Part II. A polarographic investigation

Polarographic current—potential characteristics and current—time curves for the reduction of riboflavin (RF) to dihydroriboflavin (DRF) in 0.01 M HClO₄ + 0.09 M NaClO₄ have been examined in detail. It has thus been shown that the RF adsorption prewave is due to the formation of two overlapping adsorbed monolayers of DRF molecules. Lateral interactions of RF molecules between themselves, of DRF molecules between themselves and of RF with DRF molecules in the first adsorbed monolayer are weak, whereas vertical interactions between overlapping DRF molecules are relatively strong. This explains the abrupt increase in the slope of the RF adsorption prewave and its shift towards more positive potentials as soon as the second adsorbed monolayer of DRF starts to form. The so-called “normal” wave for RF reduction has a half-wave potential E^II_{$\text{1}\text{2}$} = ?0.180 V/SCE, practically coinciding with the formal potential of the RF/DRF couple, and a slope corresponding to a reversible two-electron reduction unaffected by semiquinone formation. The shape of polarographic mean current vs. potential curves has been accounted for through an approximate solution of the corresponding diffusional problem.     

Effect of substituents on the polarographic behaviour of α-arylhydrazononitriles: Further evidence for the mechanism of polarographic reduction of α-arylhydrazononitriles

The polarographic behaviour of the α-arylhydrazonomesoxalonitrile derivatives (IIb-i) and of 2-arylhydrazono-3-keto-3-phenylpropionitriles (IIIb-f) was investigated. With the exception of the nitro-substituted derivatives IIh, i and IIIf all the investigated compounds showed polarographic waves similar to that of their respective parent compounds IIa and IIIa. The m-nitro derivatives IIh and IIIf were firstly reduced in a 4 e wave to the corresponding hydroxylamino derivatives which were subsequently reduced in the manner common to other α-arylhydrazononitriles. On the other hand, the p-nitro derivative IIi was first reduced to the hydroxylamino derivative which then lost water to yield the corresponding quinoneimine. Reduction of the latter product in a 2 e wave gave the p-amino derivative IIe, which then underwent 4 e reduction to p-phenylenediamine and aminomalonitrile. The E_1/2 values corresponding to reduction of the arylhydrazonic moiety of compounds IIa-i and IIIa-f at different pH values were correlated to Hammett's different sigma sets. Analysis of the results provided evidence for the suggested mechanism for reduction of these compounds.     

The six-membered annulation reaction involving sequential palladium-catalyzed allylic alkylation and Michael addition: scope and limitations

The palladium-catalyzed condensation of a variety of active methylene compounds with methyl 6-acetoxymethyl-hepta-2,6-dienoate was investigated. The six-membered adducts resulting from a η³ palladium complex alkylation-Michael addition sequence were obtained with moderate to good yields. In some cases, further evolution of the primary adduct was observed. The process has been expanded to access nitrogen heterocycles by using sodium p-toluenesulfonamide as the nucleophilic partner.     

Study of the electrochemical behaviour of metaclazepam in aqueous media and its determination in biological fluids

Summary The polarographic behaviour of metaclazepam in Britton Robinson universal buffer has been investigated by the following techniques: DC tast and differential pulse polarography, cyclic voltammetry, microcoulometry and adsorptive stripping voltammetry. The compound is polarographically active over the entire pH-range, showing a single well-defined wave. This has been characterized as being a 2e^– diffusion-controlled wave in acid media. The reduction step is due to the C=N group. The drug is also surface-active and the adsorption at the electrode is higher in alkaline than in acid media. A stripping method for the determination of this psychotropic drug at the sub-micromolar and nanomolar concentration levels is described. Adsorptive accumulation for 300 s followed by differential pulse measurement in Britton Robinson buffer at pH 9.1 can be used for the determination of metaclazepam in urine with an accuracy and precision of 2% and 3%, respectively. The detection limit was 0.55 ng per ml of urine (adsorptive accumulation at –0.60 V for 300 s).