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.     

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.     

Polarographic study of uracil derivatives

Eighteen uracil derivatives were studied by d.c. polarography, differential-pulse (d.p.)polarography and d.p. cathodic stripping voltammetry. In a borax buffer at ca. pH 7.6, uracil, thymine and derivatives such as 5-halouracils, 5-trifluoromethyl-,5-aza-,5-acetyl-, 5-formyl- and 5-vinyl-uracil produced well-defined peaks at potentials between 0 V and ca. 160 mV vs. silver/ silver chloride (satd. KCl). The peaks are ascribed to the formation of sparingly soluble mercury salts. For the other derivatives tested (e.g., 5-nitro- and 5-ethynyl-uracil and 6-substituted uracils), the peaks were less well-defined and in some cases the polarographic curves were very complex. 2-Thiouracil produced a single peak at ca. ?400 mV, but only at pH 12.2. The shapes, heights and potentials of the peaks depended on the kind and position of the substituent on the pyrimidine ring. Rectilinear relationships of peak current vs. concentrations were found for most compounds (10^?5-10^?4 M) by d.p. polarography; d.c.polarography was not tested quantitatively. For 5-fluorouracil and 5-vinyluracil, linear calibrations were found for concentrations of 0.5–5 × 10^?7 M by d.p. cathodic stripping voltametry. Interference studies showed that small amounts of chloride and phosphate did not interfere but 5-fluorodeoxyuridine, which did not itself produce a peak, and proteins interfered seriously.     

4.50—Polarographic investigation of conformational changes of human serum albumin: Part I. Unfolding of human serum albumin by urea

The mechanism of the unfolding of human serum albumin by urea was studied using d.c. polarography. It was found that this reaction is a complex process which cannot be described in terms of a two-state transition model. As well as the Brdi?ka catalytic current we have also studied the reduction current of disulfide groups in native and denatured human serum albumin. The number of cystine residues accessible for electrode reduction in native and denatured protein was calculated. On the basis of these results a scheme for the unfolding of human serum albumin by urea is proposed.     

Interactions of nucleic acids with electrically charged surfaces: Part IV. Local changes in the structure of DNA adsorbed on mercury electrode in the vicinity of zero charge

The influence of the interaction of double-stranded (ds) deoxyribonucleic acid (DNA) with a mercury pool electrode (MPE) on the DNA double-helical structure was investigated after a 7-hour interaction of a solution of intact calf thymus DNA with MPE. on the other hand, the contact of DNA degraded by ultrasound- and gamma-radiation with MPE charged to potentials in the region from ?0.2 to ?0.8 V led to irreversible formation of singlestranded DNA. The presence of the single-stranded DNA in a solution that had been in contact with MPE for 70 min was detected by means of u.v. spectra in the presence as well as in the absence of formaldehyde and by means of differential pulse polarography. The interaction of non-degraded DNA with MPE was studied in the presence of formaldehyde, with an aim to detect eventual reversible changes in the DNA structure. From the dependence of the rate of the reaction of DNA with formaldehyde it followed that an opening of the double-concluded that besides relatively slow surface denaturation in a narrow region of potentials at about ?1.2 V (against SCE) described earlier, a more rapid process took place in a broader range of potentials, the results of which were also changes in DNA conformation. These changes include an opening of the double helix and an easier exposition of the bases to the surrounding medium, but they are limited to only a very small part of a DNA molecule.     

Pulse polarograpmc study of the electrochemical reduction of lucigenin in aqueous medium

The electrochemical reduction of lucigenin (bis-N-methylacridinium nitrate) in aqueous solution was studied by normal pulse polarography, normal pulse polarography with differential detection of the current, and differential pulse polarography with cathodic and anodic pulses at several pulse amplitudes. The effects of pH and lucigenin concentration were studied. In confirmation of an earlier d.c. polarographic study, lucigenin is shown to be reduced in two separate one-electron steps. An adsorption peak accompanies the first step, while the second, below pH 3.5, is catalytic owing to chemical regeneration of the intermediate reduction product at the electrode surface.     

A polarographic and spectral study of some C- and N-nitroso compounds.

A wide range of N-nitroso compounds was investigated polarographically and spectrophotometrically. In general, the =N-N0 group is reduced in a 4-electron step in acidic media, which is most suitable for differential pulse polarographic analysis at the trace level. If the groups R and/or R' attached to the nitrosamine group are saturated entities, then the resulting differential pulse polarographic peaks are broad and of little use in the resolution of mixtures. The limit of detection is of the order of 10^-6M. If R and R' are unsaturated, the polarographic peaks are much sharper, mixtures can be resolved and the limit of detection is of the order of 10^-7M, C-Nitroso and C-nitro compounds are best determined by differential pulse polarography, because the waves are comparatively large and sharp, and because the reductions occur at relatively positive potentials where co-extractible interferences from foods, etc., will interfere to a minimal degree.     

Polarographic procedures without removal of oxygen, and other approaches to making the determinations more rapidly

One disadvantage of conventional d.c. polarography as an analytical method has always been its relative slowness. The possibility of simplifying and speeding up analyses by avoiding the necessity for removal of oxygen is demonstrated under suitable conditions with current-sampled d.c., pulse and a.c. polarography. In particular it is shown that high-frequency phase-selective a.c. polarography gives considerable discrimination against the oxygen electrode process in some aqueous media. Under these conditions, the high-frequency a.c. technique can be combined with the method of short drop-time, fast scan-rate rapid a.c. polarography to provide a most attractive method of routine analysis. Polarographic analysis in non-aqueous media without removal of oxygen is also discussed.     

The Use of Differential Pulse and D.C. Polarography in the Analysis of Solutions Containing Surfactants

Abstract

Peak currents in differential pulse polarography (DPP) are often used for quantitative analysis. In the presence of surfactants, peak currents depend not only on the concentration of the electroactive species, but also on that of the surfactant. In the presence of surfactants of biological origin, limiting currents obtained by d.c. polarography are often less sensitive to the effects of surfactants and are more suitable for quantitative analysis than DPP peak currents. Effects of surfactants on DPP curves were demonstrated for 4-nitrobenzoic acid in the presence of oligomers resulting from washing lignin preparations with water. In the study of adsorption of nitro compounds on lignin, d.c. polarographic curves yielded reliable adsorption isotherms whereas DPP peak currents indicated erroneously much stronger adsorption of nitro compounds on lignin.     

依来铬红B的电还原

本文用普通极谱、脉冲极谱、循环伏安法研究了依来铬红B的电还原。随着pH不同,共可产生3个波(pH6.2—12.2)。总波高相当于—受扩散控制的不可逆2电子还原波;第一波和第三波分别为吸附前波和吸附后波。根据实验结果,提出—电还原机理。     

On the electroreduction of 4-chloro-2,6-diisopropylamino-s-triazine (propazine) on mercury electrodes

This paper presents a polarographic (dc and differential pulse (DP)) study of the reduction of the s-triazine derivative propazine (4-chloro-2,6-diisopropylamino-s-triazine). The study is performed in acidic media (from solutions 2.25 M in H₂SO₄ to pH 5) because no signals were obtained above pH 5 (even at pH values of 11–12). In the pH range 2–4 the polarograms decreased until they vanished. In DP polarography, two main reduction peaks were observed, accompanied by a pre-peak at less negative potentials, and a post-peak at more negative potentials, due to the adsorption of propazine on the electrode. The main peaks corresponded to two-electron reduction processes. At pH below the protonation pK of the triazine ring (about 1.7), the results showed that, in a first stage, propazine suffers a cleavage of the Cl atom via a CEC process (electron transfer placed between two chemical reactions) to yield a dechlorinated intermediate, which is reduced through an irreversible two-electron process, the rate-determining step (r.d.s.) being the second electron transfer. At pH above the pK, a protonation of the triazine ring precedes the reduction process, this reaction being also responsible for the observed decrease in limiting current.     

溴甲酚紫的极谱研究

溴甲酚紫是一应用广泛的有机式剂^[1-4]。关于羟基三苯甲烷类染料的极谱研究报导不多^[5]。Ghoneim^[6]曾报导溴甲酚紫在pH<7时产生一个2电子还原波,当pH大于10时,可产生两个1电子还原波。Goel^[7]只研究了第一波的还原机理。本文用普通极谱、脉冲极谱、循环伏安等方法较详细地研究了溴甲酚紫的电还原。提出一电还原机理,解释了半波电位随pH变化的特殊规律。     

Contribution a l'électrochimie des thiols et disulfures : Partie I. Cystéine et cystine

A study of the electrochemical characteristics of cysteine and cystine was carried out by d.c., a.c. and differential pulse polarography. Up to three waves were observed depending on the concentration and pH. The waves of the two amino acids could be separated in a borate buffer of pH 9.2. Differential pulse polarography made it possible to determine as little 0.12 mg of cysteine and 0.24 mg of cystine per litre.     

Methods for potentiostatic evaluation of heterogeneous kinetic parameters in the presence of an irreversible following chemical reaction

A theoretical study of Brdi?ka's adsorption waves and of the corresponding i-E curves in cyclic voltammetry and E-t curves in chronopotentiometry is presented under the following conditions: (a) the electrochemical reaction 0+ne?R is reversible; (b) both the oxidized and the reduced forms are strongly adsorbed; (c) the adsorption is rapid; (d) allowance is made in the isotherm for interactions between the molecules (Frumkin type isotherm). One mathematical function and its derivative are sufficient to describe the results in the three cases. The equations derived account in particular for the following experimental characteristics: (1) the linear variation of the half-wave potential of the adsorption wave (or of the chronopotentiogram) and of the voltammetric peak potential with the concentration c; (2) the changes in the slope of the wave when c varies and the discontinuous increase of current which is observed for high concentrations; (3) the changes in peak width and the hysteresis phenomenon observed in cyclic voltammetry; (4) the S-shaped experimental chronopotentiograms; (5) the appearance of prewaves (or postwaves) in cases where both O and R are equally adsorbed; (6) the fact that prewaves or postwaves usually appear for large molecules. The results show that the appearance of a Brdi?ka prewave or postwave is often caused by energy effects arising from the interactions between adsorbed molecules, rather than by energy effects caused by interactions with the electrode surface.     

Determination of pseudouridine at submicromolar concentrations by cathodic stripping voltammetry at a mercury electrode

Pseudouridine (5-ribosyluracil), uridine (N,1-ribosyluracil), deoxyuridine (N,1-deoxyribosyluracil) and uracil are investigated by means of d.c. polarography and by differential and normal pulse polarography. Pseudouridine, which is known to be a cancer marker, yields anodic polarographic currents in the pH range 7–11, whereas uridine and deoxyuridine are inactive under the same conditions. The polarographic response of pseudouridine obtained is due to the formation of a sparingly soluble mercury compound. Pseudouridine can be determined by differential pulse polarography in the concentration range 2–6 × 10^?6 M and by differential-pulse cathodic stripping voltammetry at concentrations two orders of magnitude lower. Small excesses of uridine, deoxyuridine or proteins do not interfere with the determination.     

The analytical performance of direct current,normal pulse and differential pulse polarography with static mercury drop electrodes

The recently developed static mercury drop electrode (SMDE) provides a fundamentally new approach to electrodes for polarography. An analytical evaluation of the electrode is presented. For a range of electrode processes, current-sampled d.c. polarography at the SMDE is useful down to at least the 10^-7 M concentration level when short drop times and fast potential scan rates are used. The improvement in the limit of detection for d.c. polarography is therefore very substantial. Improvements in sensitivity associated with normal pulse and differential pulse polarography at the SMDE compared with the dropping mercury electrode (DME) are marginal. It is concluded that at the SMDE, the analytical performance and response characteristics of d.c., normal pulse and differential pulse polarography tend to converge.     

Current-sampled polarographic techniques for the measurement of species reduced at more negative potentials than the major component

With conventional d.c. polarography. a particular depolarizer cannot be determined accurately in the presence of a considerable concentration of another species which is reduced at more positive potentials. Current-sampled read-out has been suggested previously to improve the situation; this idea has now been tested experimentally. The read-out of Tast (current-sampled), derivative Tast and pulse polarographic techniques permits determinations of this type to be achieved accurately and conveniently over quite a wide concentration range, provided that a three-electrode potentiostat is used to minimize ohmic iR drop effects. The maximal concentration and the limiting concentration ratio of the two depolarizers were generally fixed more by instrumental than chemical limitations, although at very high concentrations of the major species some evidence of electrochemical interference was found.     

A polarographic study of some N-oxygenated products of N-ethyl-β-methoxy-β-(3'-trifluoromethylphenyl)-ethylamine (sk and f 40652a)

The polarographic behaviour of N-hydroxy-β-methoxy-β-(3'-trifluoromethylpbenyl)-ethylamine, N-ethyl-N-hydroxy-β-methoxy-β-(3'-trifluoromethylphenyl)ethylamine and (3-methoxy-β-(3'-trifluoromethylphenyl)acetaldoxime has been studied over the pH range 0—14. The hydroxylamines gave rise to anodic and cathodic behaviour whereas the oxime gave only a cathodic wave. The mechanism of the oxidation and reduction processes was investigated by d.c. polarography and preparative micro-coulometry. The optimum pH values for analytical purposes were 7, 8 and 4 for the two hydroxylamines and the oxime, respectively. The polarographic behaviour of a mixture of the three compounds was studied and the determination of traces of such compounds by differential pulse polarography is discussed.     

Electroanalytical studies of the pesticides menazon and its hydrolysis products

An electroanalytical study based on d.c. polarography, differential pulse polarography (d.p.p.) and coulometry is described for Menazon, S-[4, 6-diamino-1,3,5-triazin-2-yl)- methyl]-O,O-dimethylphosphorodithioate, and its alkaline hysdrolysis products in a (1 + 4) methanol/water medium. The responses of the different species are studied for analytical utility. Menazon itself produces two diffusion-controlled cathiodic waves or peaks at pH 4.78; the determination limit is 5.5 × 10^-7 M for the d.p. peak at about ?0.8 V vs. Ag/AgCl. The hydrolysis products obtained in 0.1 M sodium ydroxide give rise to four anodic waves. Acidification of the alkaline medium to pH 4.3 produces three well-defined waves; two cathodic and one anodic. The responses for the cathodic processes are linear with concentration over 2–2.5 orders of magnitude; the anodic wave is adsorption-controlled and provides linear response only at low concentrations. The detection limit for the hydrolysis products is 0.17 × 10^-6 M. Reaction mechanisms are proposed.