Calculation of differential pulse polarographic curves for the reduction of complexes

A simple simulation is presented which allows calculation of differential pulse polarographic (DPP) curves for reversibly reduced complexes, applicable to all concentrations of ligand and to mixtures of up to four complexes. The simulation is employed to investigate the expected forms of DPP curves as a function of the values of overall formation constant (β_p) and ligand concentration.For a single 1:2 complex a splitting of the DPP curve is predicted at substoichiometric ligand concentrations for log β₂ values > ca. 10. These systems exhibit one peak at E° for the metal and a second broadened peak at a more negative potential.At stoichiometric ligand concentrations broad peaks are predicted which shift in potential with β_p in a predictable manner above a characteristic value of β_p.Assumed mixtures of two complexes at ligand concentrations substoichiometric with respect to the higher complex exhibit one or two peaks, with potentials and shapes dependent on the two β_p values.A method is proposed for the determination of the first formation constant in mixtures of two complexes, based on measurement of differences in peak potentials.     

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.     

Electrochemical behavior of 2'-halogenated derivatives of N,N-dimethyl-4-aminoazobenzene at mercury electrode.

The electrochemical behavior of 2'-halogeno-N,N-dimethyl-4-aminoazobenzene derivatives was investigated using various polarographic and voltammetric methods. The peak potentials of these derivatives were observed to shift towards negative values along with an increase in the pH. A reduction of the azo linkage took place via two electrons at pH > 4, but four electrons at pH < 4 in aqueous-ethanol mixtures. The standard rate constants were determined with (Laviron technique) or without (Nicholson technique) taking the adsorption phenomena into account. The diffusion coefficients were calculated from the cyclic voltammetric data using a method developed by Garrido. The amount of adsorbed substances and transfer coefficients for the electron transfer were also determined. A mechanism for the electrode reaction is proposed. These compounds can be quantitatively determined between 1 x 10(-5) M and 1 x 10(-7) with DPP and CV.     

氮氧自由基研究:XXI,水溶液中哌啶氮氧自由基单电子还原反应机理的极谱研究

本文采用取样直流极谱, 常规脉冲极谱, 微分脉冲极谱和交流极谱考察了,2,2,6,6-四甲基-4-羟基哌啶 -1-氧和2,2,6,6-四甲基-4-氧哌啶 -1-氧由基及2,2,6,6-四甲基哌啶 -1-氧自由基在水溶液中的还原反应, 并研究了它们的还原经历电化学过程 。     

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.     

Simultaneous electrochemical determination of three sunscreens using cetyltrimethylammonium bromide

This paper proposes a methodology based on electrochemical reduction for the simultaneous determination of three sunscreen agents, namely 4-methylbenzylidene camphor (MBC), benzophenone-3 (BENZO) and 2-ethylhexyl-4-methoxycinnamate (EHMC) by differential-pulse polarography (DPP). The highest peak currents and optimal separation of reduction peaks were obtained by using a supporting electrolyte consisted of Britton-Robinson buffer-methanol (8:2) solution at pH 4.0 and cationic surfactant 3.0 x 10(-4)mol L(-1) cetyltrimethylammonium bromide (CTAB). The methodology was validated using four commercial sunscreen preparation as a sample and the results showed high recovery rates. The efficiency of the proposed methodology was demonstrated by comparing the results obtained by DPP with those obtained by the high-performance liquid chromatography (HPLC) method.     

Electrochemical and microsomal production of free radicals from 1,2,5-oxadiazole N-oxide as potential antiprotozoal drugs

The electron spin resonance (ESR) spectra of free radicals obtained by electrolytic or microsomal reduction of several potential antiprotozoal 1,2,5-oxadiazoles were characterized and analyzed. Ab initio molecular orbital calculations were performed to obtain the optimized geometries and the theoretical hyperfine constant was carried out using ZINDO semiempirical methodology. Density functional theory was used to rationalize the reduction potentials of these compounds.     

Electrochemical and spectroscopic characterization of interaction between antimalarial drug cinchonine and human serum albumin at physiological pH

In the present study, the interaction between cinchonine (CCN) and human serum albumin (HSA) was investigated using differential pulse polarography (DPP), cyclic voltammetry (CV) and spectroscopic techniques in Britton-Robinson (B-R) buffer pH 7.4. CCN displayed a main cathodic peak at ?1.228 V (vs. Ag|AgCl|KCl_sat) on mercury working electrode. The addition of HSA into CCN sulfate solution resulted in the decrease of the main reduction peak current of CCN and no new peaks appeared. The decay in the peak current of CCN, after the addition of HSA, showed a decrease in free drug concentration and formation of a biocomplex. The peak current changes of CCN in the presence of HSA were followed by DPP to determine the binding parameters. The logarithm of binding constant and binding ratio between CCN and HSA were 6.128 and 1: 1, respectively. This interaction was also confirmed by UV-Vis and FTIR-ATR spectroscopic measurements.     

Voltammetric behavior of zaleplon and its differential pulse polarographic determination in capsules

In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography.     

Identification of iron(III) oxides and hydroxy-oxides by voltammetry of immobilised microparticles

In this paper, we propose the use of an electroanalytical technique based on the direct oxidation or reduction of the electroactive components of the sample on the surface of the working electrode, called voltammetry of immobilised microparticles (VMPs). The sample is easily deposited on the electrode by abrasion and then the electrode is transferred to the electrochemical cell where the square wave potential scan is performed. Electroactive species showed peaks whose peak potential is related to the standard formal potentials. We applied this technique to the identification of iron oxides and hydroxy-oxides in cosmetics. To characterise and identify the iron(III) oxides and hydroxy-oxides VMP was performed in two different media: oxalic acid and hydrochloric acid, that is, a complexing and a slightly complexing media. Two electrode processes were observed. They were influenced by the media and the synthesis procedure of the oxides. The reduction peak at negative potentials (−0.50 V in hydrochloric acid and −0.60 V in oxalic acid) is related to the direct reduction of the iron(III) oxide and it does not appear in the case of the more reactive phases (hydroxy-oxides). The peak at positive potentials (0.90 V in hydrochloric acid and 0.60 V in oxalic acid) involves the reduction of iron(III) in solution. The same electrode process were observed for binary mixtures but the peak potentials are shifted from the pure components peak potentials. This allowed us to distinguish between their mixtures. Finally, VMP was used to characterise iron oxides in cosmetic powders.     

Tuning phenoxyl-substituted diketopyrrolopyrroles from quinoidal to biradical ground states through (hetero-)aromatic linkers

Strongly fluorescent halochromic 2,6-di-tert-butyl-phenol-functionalised phenyl-, thienyl- and furyl-substituted diketopyrrolopyrrole (DPP) dyes were deprotonated and oxidised to give either phenylene-linked DPP1˙˙ biradical (y₀ = 0.75) with a singlet open shell ground state and a thermally populated triplet state (ΔE_ST = 19 meV; 1.8 kJ mol⁻¹; 0.43 kcal mol⁻¹) or thienylene/furylene-linked DPP2q and DPP3q compounds with closed shell quinoidal ground states. Accordingly, we identified the aromaticity of the conjugated (hetero-)aromatic bridge to be key for modulating the electronic character of these biradicaloid compounds and achieved a spin crossover from closed shell quinones DPP2q and DPP3q to open shell biradical DPP1˙˙ as confirmed by optical and magnetic spectroscopic studies (UV/vis/NIR, NMR, EPR) as well as computational investigations (spin-flip TD-DFT calculations in combination with CASSCF(4,4) and harmonic oscillator model of aromaticity (HOMA) analysis). Spectroelectrochemical studies and comproportionation experiments further prove the reversible formation of mixed-valent radical anions for the DPP2q and DPP3q quinoidal compounds with absorption bands edging into the NIR spectral region.

By variation of spacer aromaticity, a spin crossover from thienylene/furylene-linked quinones DPP2q/DPP3q to phenylene-bridged biradical DPP1˙˙ (y₀ = 0.75) with a singlet open shell ground state (ΔE_ST = 19 meV) was achieved.     

Determination of traces of molybdenum and tungsten by extraction and polarography of their salicoylhydroxamates

Molybdenum and tungsten salicoylhydroxamates have been extracted into methyl isobutyl ketone or a mixture of chloroform and isobutyl alcohol from 1.5M hydrochloric acid and subjected to DC and derivative pulse polarography (DPP) after addition of methanolic lithium chloride solution, phosphoric acid and water in defined proportions. Molybdenum gives two DC waves with E(1 2 ) at -125 and -525 mV and a sharp DPP peak at -75 mV, whereas tungsten shows a single DC wave at -840 mV and a DPP peak at -850 mV. The two metals can be determined down to the sub-ppm level.     

Extended Conjugated Donor–Acceptor Molecules with E‐(1,2‐Difluorovinyl) and Diketopyrrolopyrrole (DPP) Moieties toward High‐Performance Ambipolar Organic Semiconductors

Two diketopyrrolopyrrole (DPP)‐based donor–acceptor (D–A) conjugated molecules, DPP‐F and DPP‐2F, which contain E‐(1,2‐difluorovinyl) moieties, are reported. The LUMO energies of DPP‐F and DPP‐2F were estimated to be ?3.49 and ?3.70 eV, respectively, based on their redox potentials and absorption spectral data; these values were clearly lowered because of the incorporation of electron‐withdrawing E‐(1,2‐difluorovinyl) moieties. Organic field‐effect transistors (OFETs) with thin films of DPP‐F and DPP‐2F were successfully fabricated with conventional techniques. Based on the respective transfer and output characteristics measured in an inert atmosphere, thin films of DPP‐2F display ambipolar semiconducting behavior with hole and electron mobilities reaching 0.42 and 0.80 cm² V^?1 s^?1, respectively. The as‐prepared OFET of DPP‐2F already shows high hole and electron mobilities that are not influenced remarkably by thermal annealing. For thin films of DPP‐F, only p‐type semiconducting behavior was observed in both an inert atmosphere and air, and the hole mobility increased to 0.1 cm² V^?1 s^?1 after thermal annealing. XRD and AFM studies were performed with thin films of DPP‐F and DPP‐2F after annealing at different temperatures.     

Electrochemical behavior of mesoionic sydnone derivatives at wax-impregnated carbon paste electrode

The-N=N-moiety in the mesoionic 3-phenyl sydnone and its derivatives like tolyl sydnones and anisyl sydnones undergo two-electron irreversible electrochemical reduction in Britton-Robinson (BR) buffer at wax-impregnated carbon paste electrodes. Infrared, nuclear magnetic resonance, and mass-spectral data, used to characterize the reduced product, confirm the proposed mechanism. The pasting liquid at the surface of the electrode is found to decrease the electron-transfer rate and cause a higher overpotential compared to homogeneous electrodes. The influence of variation of pH on the peak current and peak potentials is studied in the acidic range. The cathodic peak shifts to more negative potentials with increase in pH, indicating the involvement of proton in the reduction process. This could be a new method of preparation of 2,4-dihydro-3-substituted 1,2,3-oxadiazole-5-one. The substituent effect and the effect of variation of scan rate, concentration, and temperature on peak currents and peak potentials is discussed. The cathodic shift in various organic co-solvents (methanol, acetonitrile, DMF, DMSO) using BRB as the supporting electrolyte is examined. Published in Russian in Elektrokhimiya, 2006, Vol. 42; No. 7, pp. 862–868. The text was submitted by the authors in English.     

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.     

Studies on the Complexation of Transition Metal Ions with Macrocyclic Compounds in Mixed Solvents by Competitive Potentiometry and Polarography

Complexation of Cu(II), Zn(II), Ni(II), Co(II), Pb(II), Cd(II), Cr(III) and Fe(III) ions with 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, dibenzo-24-crown-8, 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene, 1,4,10-trioxa-7,13-diazacyclopentadecane and cyclam has been investigated in 75% (v/v) DMF+water using the silver(I) ion as an auxiliary cation at 0.05?M ionic strength adjusted with tetrabutylammonium perchlorate (TBAP) by competitive potentiometry. Stability constant values obtained for the metal ion–aza macrocyclic complexes are higher than those for the oxa crowns. Shifts in the peak potential and reduction in the peak current in the differential pulse polarography (DPP) method were also used to determine the stability constants of some of the metal ions with aza and tosylated-aza macrocycles using TBAP as supporting electrolyte in 75% (v/v) DMF+water and 90% (v/v) DMSO+water media. Stability constant values determined both by shifts in the potential and by reduction in the peak current were found to be in good agreement with each other.     

Voltammetric reduction of finasteride at mercury electrode and its determination in tablets

Finasteride in hydroalcoholic solutions (ethanol/Britton-Robinson buffer, 30/70) exhibits cathodic response in a wide range of pH (-0.5 to 12) using differential pulse (DPP) and test polarography (TP). The reduction peak of finasteride at acidic pH, is a catalytic proton peak resulting from a mechanism involving a first protonation of finasteride followed by the reduction of the protons combined with finasteride in order to regenerate finasteride and liberate hydrogen. Based on the catalytic hydrogen wave, a novel method for the determination of finasteride can be proposed. For analytical purposes we selected DPP technique in an ethanol/0.0625 mol L(-1) H(2)SO(4) (30/70) solution medium. In this condition the I(p) varied linearly with finasteride concentration between 5 x 10(-5) and 5 x 10(-4) mol L(-1). Within-day and inter-day reproducibility's were adequate with R.S.D. values lower than 2%. The selectivity of the method was checked with both accelerated degradation trials and typical excipients formulations. The developed method was applied to the assay and the uniformity content of finasteride tablets and compared with the standard HPLC method. The DPP-developed method was adequate for the finasteride determination in pharmaceutical forms as that exhibited an adequate accuracy, reproducibility and selectivity. Furthermore, treatment of the sample was not required as in HPLC; the method is not time-consuming and less expensive than the HPLC ones.     

Differential-pulse polarography (DPP) determination of betamethasone valerate in dosage form

The electrochemical reduction of betamethasone valerate (BV) in a pharmaceutical formulation containing neomycin has been carried out in Britton-Robinson buffer (BRB) (0.04 mol L(-1)) by differential-pulse polarography (DPP). BV exhibits a well-defined irreversible reduction peak at -1.03 V/ref. The influence of pH on the reduction of BV was studied in Britton-Robinson buffer (pH range 1.7-10). A method for the analysis of BV in BRB (0.04 mol L(-1)), which allows quantification over the range 3.9x10(-6)-1.1x10(-4) mol L(-1), was proposed and successfully applied to the determination of BV in tablets with mean recovery and relative standard deviation of 100.81% and 0.45%, respectively.     

In-Situ Electron Spin Resonance Studies of Polyaniline

In-situ electron spin resonance studies of polyaniline at various applied potentials in media of pH 0.49, 2.09, 3.96, anf 9 are reported. The g factor of the esr signal is 2.0036 and does not vary with the applied potential. The peak to peak linewidth decreases to a minimum in a potential range which depends on the pH of the medium. On the other hand, the spin density increases to a maximum in the same potential range. The pH-potential range where the highly conductive form exists, matches very well the range of narrow linewidth and high spin density of the esr signal. The conductive form of polyaniline consists of highly mobile radical cations or polarons.     

Simultaneous determination of In(III) and Cd(II) by differential pulse polarography in the presence of poly β-cyclodextrin

The difference in the peak potentials of In(III) and Cd(II), whose reduction potentials are very close to each other, becomes large in the presence of poly beta-cyclodextrin in sodium perchlorate medium. The relationships between the peak currents for these two ions and their concentrations are linear, suggesting that the simultaneous determination of the ions is possible in the presence of this reagent.