Effects of surfactants in differential pulse polarography

Differential pulse polarograms of surfactants exhibit tensammetric peaks at the adsorption and desorption potentials of the surfactant. In the potential range where adsorption occurs the base current is depressed. The heights of the tensammetric peaks are nonlinear functions of the bulk concentration of the surfactant. Differential pulse polarograms of reducible substances are greatly affected by the presence of surfactants, the effect being similar to that observed in a.c. polarography. Surfactants with the same charge as the depolarizer act as electrochemical masking agents, whereas peak currents may be enhanced by oppositely charged surfactants.     

Reactant adsorption in analytical pulse polarography: An outline in terms of the concentration profile

The consequences of adsorption of the electroactive species in analytical pulse polarography are discussed. For both normal pulse polarography (NPP) and differential pulse polarography (DPP) explanations are given in terms of the concentration profiles as they are developed upon adsorption before pulse application. An approximate interpretation of the depressed NPP limiting current is sometimes possible by taking its dependence on pulse duration into account. In a number of cases NPP offers the possibility of avoiding adsorption effects by choosing a suitable initial potential. In DPP reactant adsorption generally causes peak enlargement, but the theoretical approach is complex and practical means for checking or eliminating adsorption effects in DPP are limited. Analytical calibration curves start with a linear portion corresponding with the linear adsorption regime; at higher concentrations the DPP curve bends downwards, whereas the NPP curve bends slightly upwards, before reaching the linear region of diffusion control. Several analytical pitfalls connected with the adsorption phenomena are indicated.     

Polarographic Study of Lead-Tropolone Complexation

Abstract

A.C., D. C. and derivative pulse polarography of lead-tropolone complexes has been studied. It has been shown that the application of usual treatments for complexation in d. c. polarography are invalid in this system, where the irreversible wave in presence of the ligand is a composite step. It seems generally advisable to apply derivative pulse or a.c. polarography before using non-reversible d.c. steps for evaluation of K and p.     

Biamperometric and Differential Pulse Polarographic Methods for the Assay of Nomifensine Maleate

Abstract

Biamperometric titration and differential pulse polarography (DPP) are described for the analysis of nomifensine maleate powder and commercial capsules (Merital^R -50 mg). The biamperometric method involved the titration in cold dil. HCl medium against 0.01 M - NaN0₂ and electrometric detection of end point. The mean percent recoveries obtained were 100.0 ± 0.87 and 99.2 ± 0.95 for the authentic powder and capsules, respectively. The DPP method was performed by measuring the peak current, i_P, obtained from the recorded differential polarogram under constant 50mV modulation amplitude. The peak current was measured at the peak potential of ? 1.02 V on the dropping mercury electrode (DME) versus Ag/AgCl/KCl (sat.) reference electrode at pH 5.0 (acetate buffer). A linear relationship between peak current and concentration was demonstrated in the range 3 to 30μg ml^?1. The mean percent recovery for the capsules was 103.1 ± 1.26.     

Determination of Methylmercury by Phase-Sensitive A. C. Polarography

Abstract

The polarographic reduction of methylmercury in aqueous medium takes place in two steps, each of which involves the transfer of a single electron. The first reduction step proceeds reversibly both in direct current and in sinusoidal alternating current. Since the polarograms corresponding to this step are well defined, they can be successfully used to determine methylmercuric compounds by phase-sensitive sinusoidal a.c. polarography, in the concentration range 1 × 10^?7 ?1 × 10^?4 mole.dm.^?3     

Electrochemical studies of berberine and jatrorubine by pulse polarography

The application of pulse polarography (PP) and differential pulse polarography (DPP) for the quantitative determination of berberine and Jatrorubine in aqueous, acidic solutions was investigated. The proposed methods could be successfully applied in the concentration range between 5·10^–7 (DPP) or 1·10^–6 (PP) and 5·10^–5 mol/dm³ of alkaloids.     

Determination of Methimazole and Carbimazole Using Polarography and Voltammetry

Abstract

Anodic waves of methimazole (I) (1-methylimidazole-2-thiol) and carbimazole (II) (1-ethoxycarbonyl-3-methyl-2-thio-4-imidazoline) on mercury electrodes correspond to mercury salt formation. Both compounds form in the thiono form a soluble complex at pH < 6, compound (I) at higher pH-values a slightly soluble salt of the thiol form. Electrode processes involving the thiol form are complicated by adsorption. Oxidation at solid electrodes occurs only at potentials more than 0.5 V more positive. For compound (I) spectrophotometry indicated pK_a=12.0 ± 0.2. By d.c. polarography in 0.1 M H₂SO₄ containing 10% ethanol the determination of both compounds is possible between 4 × 10^? and 1 × 10^?3 M, by differential pulse polarography between 1 × 10^? and 1 × 10^?4 M, by differential pulse voltammetry at HMDE between 5 × l0^?7 and 6 × 10^? M.     

Effect of methyl viologen on the electrochemical behavior of denatured cytochrome c at mercury and solid electrodes

Denatured cytochrome c has been studied in 9.5 M urea medium in the presence of methyl viologen, using differential pulse polarography (DPP) and voltammetry (DPV), alternating current polarography (ACP) and cyclic voltammetry (CV). The DPP and CV curves exhibit an additional peak, which is assigned to the catalytic reduction of denatured cytochrome c.     

Simultaneous Polarographic Determination of Lead (II) and TIN (II) by Multivariate Calibration

ABSTRACT

The polarographic waves of lead (II) and tin (II) overlap due to their similar reductive potentials and it is difficult to determine these two components simultaneously without a pre-separation. In this paper, differential pulse polarography (DPP) combined with multivariate calibration approaches, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS), were successfully applied to the resolution of overlapping polarographic waves of these two components in the concentration range of 0.05-3.50 mg 1^?1. Satisfactory quantitative results were obtained.     

Etude Polarographique De La Marcellomycine

Abstract

Polarographic study of marcellomycine.

d.c., a.c. and d.p. polarography and cyclic voltammetric techniques were used to investigate the electrochemical properties of marcellomycine. These are found to be quite similar to those of aclacinomycine or carminomycine, the main reversible two-electron wave being attributed tot he reduction of the quinonic structure. The molecule undergoes a degradation process starting in acidic medium and giving rise to the formation of two small irreversible waves at more negative potentials. This process is time, illumination and pH dependent. Important adsorption phenomena interfere in the investigated pH range but are lowered in very acidic medium. Quantitative measurements have been carried out at pH 1 and 6 in a 10^?3 to 10^?5 M concentration range using d.c. polarography. d.p. technique allows determinations in a restricted 10^?5 to 10^?4 M range. A detection limit of 1 · 10^?5 M has been fixed at pH 1.     

Determination of Chloramphenicol (CAP) in Food Products by Differential Pulse Polarography

ABSTRACT

The electrochemical determination of chloramphenicol (CAP) in food using mini- and micro- mercury drop electrodes and differential pulse polarography (DPP) has been elaborated. A phosphate buffer with pH 6.6 was used as the basic electrolyte. The analysis was based on a peak at the potential E_p = ?0.320 V which showed a clearly linear dependence of the peak current on the concentration of chloramphenicol in the sample under investigation. Prior to the determination of chloramphenicol in actual samples it was necessary to extract this antibiotic with organic solvents such as methanol, ethanol and ethyl acetate.

In order to separate CAP in its basic form, various modifications of sample preparation procedures were made for the analysis with the use of selected hydrolytic enzymes. The determined quantities of CAP in the samples of meat, milk, eggs and their products ranged in the ng/g d.w. range.

For purposes of comparison and verification of the electrochemical results of CAP determination, chloramphenicol was determined in the same samples, by the immunoenzymatic method ELISA.     

Desorption Preceding Polarographic Reduction of Some Acetophenone Derivatives in Alkaline Media

Abstract

Change in d.c. polarographic capacity currents, in a.c. polarographic curves, in electrocapillary curves, and in oscillographic dE/dt = f(E) curves indicate that ω-benzyl and ω-phenyl acetophenones are reduced at potentials at which their oxidized form is already desorbed.     

Determination of Benzoylmetronidazole in Suspension Formulations by Differential Pulse Polarography

Abstract

A rapid, reproducible and accurate method for the determination of benzoylmetronidazole in pharmaceutical suspensions is presented. Differential pulse polarography at a static mercury drop electrode is used for the reduction of the nitro group of benzoylmetronidazole.     

Polarography of 4-Nitrophthalic Acid

The–NO₂ group reduction in 4-nitrophthalic acid (NPA) at dropping mercury electrode over a wide range of _PH, is irreversible and diffusion controlled. Ill defined waves preceded the —NO₂ group wave, were observed between _PH 7 and 12 whereas at _PH 5.0, a rounded maximum appears. The a. c. reduction of NPA at _PH 12.0, provides two peaks, first peak corresponds to d. c. pre-step, is essentially due to adsorption phenomena whereas other peak is the reduction wave. Using McBain Down cell and King-cathcart equation the diffusion coefficient of NPA is 0.713×10^-3 cm²sec^-1. Six electrons are being involved in nitro group reduction and mechanism of the reduction was suggested. The kinetic parameters in absence and presence of ionic and non-ionic surfactants were determined. The reduction process becomes more and more irreversible as surface activity of organic compounds increases. Ionic surfactants are effective in increasing the value of —log K° than the non-ionic surfactants. The value of ana decreases regularly by the presence of compounds having regular increase of surface activity.     

Some basic views on the influence of reactant adsorption on wave shapes in D.C., A.C. and linear sweep voltammetry

A comprehensive discussion is presented of the basic views and quantitative expressions which are needed the understand the influence of adsorption of electroactive species on the shapes of the waves in d.c. polarography, a.c. polarography and linear sweep voltammetry. It is shown that it is either the non-stationary nature of the techniques or the non-stationary nature of the electrode surface area (or both) which shows up the influence of adsorption.     

Polarographic Determination of Aztreonam

Abstract

The polarographic behaviour of Aztreonam is studied. In acid media, at pH values lower than 6, in differential pulse polarography a peak is observed at a potential close to ? 0.6 volts. The optimum conditions for the polarographic signal are established and the different parameters affecting the electrochemical process are studied. The relationship between peak intensity and the concentration of Aztreonam is linear for concentrations lower than 1.0 ? 10^?5 M, the detection limit being 1.4 × 10^?8 M It was observed that the presence of 1-arginine does not affect the polarographic signal of Aztreonam to any significant extent.     

Pulse-polarographic analysis of nucleic acids and proteins

Nucleic acids and proteins were studied by means of derivative and normal pulse polarography, and d.c. and a.c. polarography in connection with the dropping mercury electrode. It was shown that natural ribonucleic acids, as transfer, ribosomal and viral RNAs yield derivative pulse-polarographic peaks; from their heights and potentials conclusions can be made about their content of ordered structure in solution, similarly as in the case of deoxyribonucleic acids studied earlier. Synthetic single-stranded polyribo-cytidylic acid yields a well developed peak, whereas in the double-helical complex with polyriboguanylie acid it is inactive when using either derivative pulse polarography or d.c. polarography. Well developed peaks were obtained also with albumin (a protein containing reducible?S?S? groups), while only an inflex was observed on the d.c. polarogram. Proteins were also studied in media containing cobalt (Brdi?ka's solution) or nickel and it was shown that derivative pulse polarography due to its high sensitivity and accuracy enables us to carry out the measurements even in less common media than Brdi?ka's solution. This fact could be exploited in clinical chemistry as well as in the investigation of the nature of catalytic currents of proteins. The currents of double-helical polynucleotides obtained by means of normal pulse polarography exhibit a marked dependence on the initial potential and cannot represent a reliable indicator of structural changes of biopolymers in solution. They can however, be used in studies of the influence of the polynucleotide adsorption at different potentials on the subsequent reduction.     

Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid

The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. −10° for Cd-PMA and ca. −15° for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.     

Aqueous sulfur species determination using differential pulse polarography

Sulfur species play pivotal roles in biogeochemistry; however, quantification remains difficult because such species are transitory. Our objective was to determine the utility of using differential pulse polarography (DPP) to characterize soluble sulfur species of potential interest in agriculture and environmental quality. Polarographic responses for sulfide, disulfide, pentasulfide, sulfite, thiosulfate, tetrathionate, pentathionate, cysteine, and glutathione were determined. Sulfur in the compounds was categorized as cysteine-S, thiosulfate-S, nonpurgeable or purgeable sulfide-S, or sulfite based on characteristic polarographic responses for each respective category. Nonpurgeable sulfide-S, cysteine-S, and thiosulfate-S were polarographically separated using a pH 8.0 phosphate buffer. Nitrate/bicarbonate (pH 10.0) and acetate (pH 5.0) buffers were used to determine purgeable sulfide-S and sulfite, respectively. Sulfur in water extracts from cysteine-amended soils was quantified using the developed DPP method. Cysteine-, thiosulfate-, and sulfide-S were measured from these extracts without interferences during a 16-d incubation period. The developed DPP method provides qualitative and quantitative information concerning sulfur species in aqueous solutions and is potentially applicable to soil and sediment extracts.