Electrochemical behavior and antioxidant and prooxidant activity of natural phenolics

We have investigated the electrochemical oxidation of a number natural phenolics (salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, protocatechuic acid, o-coumaric acid, m-coumaric acid, p-coumaric acid, caffeic acid, quercetin and rutin) using cyclic voltammetry. The antioxidant properties of these compounds were also studied. A structural analysis of the tested phenolics suggests that multiple OH substitution and conjugation are important determinants of the free radical scavenging activity and electrochemical behavior. Compounds with low oxidation potentials (Epa lower than 0.45) showed antioxidant activity, whereas compounds with high Epa values (>0.45) act as prooxidants.     

Electrochemical transformations and anti/prooxidant activity of sterically hindered <Emphasis Type="Italic">o</Emphasis>-benzoquinones

The electrochemical properties of a series of sterically hindered o-benzoquinones in aprotic solvents were examined. The reaction of O₂ and KO₂ with o-benzoquinones and electrogenerated o-semiquinone radical anions was studied. The formation of o-semiquinone radical anions in the reactions of KO₂ with the studied o-quinones was detected using UV-visible and ESR spectroscopy. The influence of the test compounds on lipid peroxidation was considered at the molecular and tissue levels in vitro. In the most cases, o-quinones exhibit antioxidant activity, which varies depending on the type of lipid substrate.     

邻苯二酚在活化玻碳电极上的电化学行为

邻苯二酚( QH2,儿茶酚)等有机化合物是人体内的电活性物质,直接参与人体内的各种生理过程.     

Metal-carboxylate coordination polymers with redox-active moiety of tetrathiafulvalene (TTF)

Though numerous metal-organic frameworks or polymers have been reported, the organic building blocks are usually not redox-active. On the other hand, some mono-, di- or tri-nuclear compounds with tetrathiafulvalene (TTF) have been prepared, although little is known about the coordination polymers combined with paramagnetic metals and organic TTF ligands. We report herein a series of coordination polymers of copper(II) and manganese(II) with TTF dicarboxylate ligand (L). Compound 1, [CuL(2,2-bpy)](n), is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, [MnL(2,2-bpy)](n), also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, [MnL(4,4-bpy)(H(2)O)](n)·CH(3)CN, takes a 2-D grid network. A zinc(II) compound 4, [ZnL(4,4-bpy)(H(2)O)](n)·CH(3)CN, isomorphous structure with 3, is also presented. The electrochemical properties of the solid-state compounds were investigated by cyclic voltammetry using surface-modified electrodes. As usually observed in TTF derivatives, two sets of redox-waves were observed. The values of E(1/2)(1) of compounds 1-4 are in the order of 2(Mn) ≈ 3(Mn) < 1(Cu) < 4(Zn), indicating that the metal coordination can affect the potential shift of the TTF ligand. Weak antiferromagnetic exchanges are observed for compounds 1, 2, and 3.     

Electrochemical control of the interactions of polymers and redox-active surfactants

We report the characterization of aqueous solutions (0.1 M Li(2)SO(4)) of dilute ethyl(hydroxyethyl) cellulose (EHEC) mixed with the redox-active surfactant (11-ferrocenylundecyl)trimethylammonium bromide (FTMA) by measurements of clouding temperatures and dynamic light scattering. The investigation sought to test the hypothesis that FTMA, which forms micelles in aqueous solution in its reduced state but not in its oxidized state, would permit reversible control over the formation of polymer-surfactant complexes in solution. Our measurements revealed that low concentrations of reduced FTMA enhance aggregation, whereas high concentrations of reduced FTMA disperse polymer-surfactant aggregates. This behavior is qualitatively similar to both dodecyltrimethylammonium bromide and sodium dodecyl sulfate and reflects cooperative interactions between FTMA and EHEC. In contrast, oxidized FTMA was found not to promote EHEC aggregation at low concentrations of oxidized FTMA nor disperse EHEC aggregates at high concentrations. Measurements of dynamic light scattering revealed that the reduction of oxidized FTMA in solutions of EHEC containing 0.1-0.3 mmolal FTMA causes an increase in the sizes of polymer-surfactant aggregates of more than 1 order of magnitude. Our cloud point measurements also revealed that clouding can be induced isothermally via the electrochemical reduction of oxidized FTMA at room temperature at FTMA concentrations between 0.4 and 10 mmolal. In contrast, at concentrations of FTMA greater than 15 mmolal, the reduction of oxidized FTMA induces the clearing of EHEC solutions. We conclude that aggregation of EHEC in dilute solutions can be controlled by the manipulation of the oxidation state of FTMA.     

Electrochemical behavior of catechol in the presence of 2-methyl-1,3-cyclopentanedione: application to electrosynthesis

Abstract  Electro-oxidation of catechol in the presence of 2-methyl-1,3-cyclopentanedione as a nucleophile was investigated in water–acetonitrile (90:10 v/v) solution. The results indicate that the o-benzoquinone electrogenerated participates in a Michael addition reaction with this nucleophile. The electrosynthesis of 2-(3,4-dihydroxyphenyl)-2-methylcyclopentane-1,3-dione was carried out. The product was characterized by NMR, MS, FT-IR, and elemental analysis. An EC mechanism was deduced from voltammetric and spectroscopic data. Also, the Michael addition reaction rate constant (k _m) was estimated using digital simulation of voltammograms. Graphical abstract   Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Electrochemical behavior of catechol in the presence of 2-methyl-1,3-cyclopentanedione: application to electrosynthesis

Abstract  

Electro-oxidation of catechol in the presence of 2-methyl-1,3-cyclopentanedione as a nucleophile was investigated in water–acetonitrile (90:10 v/v) solution. The results indicate that the o-benzoquinone electrogenerated participates in a Michael addition reaction with this nucleophile. The electrosynthesis of 2-(3,4-dihydroxyphenyl)-2-methylcyclopentane-1,3-dione was carried out. The product was characterized by NMR, MS, FT-IR, and elemental analysis. An EC mechanism was deduced from voltammetric and spectroscopic data. Also, the Michael addition reaction rate constant (k _m) was estimated using digital simulation of voltammograms.     

Electrochemical synthesis of polyhydroxylated aromatic derivatives substituted with mono- and dipyrimidinyl thioethers in aqueous medium

Polyhydroxylated aromatic pyrimidinyl thioethers are important compounds due to their potential anti-HIV integrase activity. The present work describes an electrochemical synthetic strategy and environmentally benign approach for the synthesis of these compounds, superior to conventional chemical reactions. Thus, the electrochemical oxidation of 4-substituted catechols and caffeic acid, in the presence of 2-mercaptopyrimidine derivatives 2, generates monopyrimidinylthio-substituted polyhydroxylated aromatics 3a–f in moderate yields. In the case of catechol itself and 3-substituted catechols, both mono- (3g–l) and dipyrimidinylthio-substituted derivatives (4g–l) were produced. Apparently, the anodic oxidation of catechol derivatives leads to nucleophilic addition products of types 3 and 4, which are different from the traditional nucleophilic substitution reaction of aryl halides and thiols. The electrochemically induced reaction mechanism is also discussed.     

Surface activity and redox behavior of nonionic surfactants containing an anthraquinone group as the redox-active site

Two new nonionic surfactants, α-anthraquinonyloxyhexyl-ω-hydroxy-oligo(ethylene oxide) (ACPEG) and α-anthraquinonyl-ω-hydroxy-oligo(ethylene oxide) (APEG), were synthesized. The fundamental interfacial behavior of these surfactants at the air/water interface has been investigated by means of surface tensiometry to provide an insight into the relationship between the structure of the hydrophobic moiety and the surfactant properties, with specific emphasis on the anthraquinone linkage. Aggregation numbers of the surfactants have been determined from static light scattering measurements. At a constant hydration of the ethylene oxide chain, the increase in the hydrophobic chain length in ACPEG raises its hydrophobic interaction and results in enhanced aggregation and significant variation in the interfacial and micellization properties compared to APEG. The electrochemical behavior of the surfactants has also been studied in 0.16 M NaCl aqueous solutions and in 0.1 M tetrabutylammonium perchlorate acetonitrile solutions at the interface of a glassy carbon electrode. A difference in the extent of aggregation has a pronounced effect on the cyclic voltammetric behavior of the surfactants in aqueous solution. In organic media, on the other hand, the redox process depends only on the molecular geometry of the monomeric species. A comparison of the electrochemical responses in the two phases has been made to explain the distinctive features of the redox properties of the surfactants. Received: 30 May 1999 Accepted in revised form: 29 June 1999     

Electrochemical behavior of catechol and 3,4-dihydroxytoluene in acetonitrile at a platinum-disk electrode modified with a tyrosinase containing polyacrylamide film.

A modified platinum-disk electrode coated with a non-plasticized polyacrylamide (PAA) membrane was used to study electrochemically an enzymatic reaction between tyrosinase in the PAA membrane and catechol and 3,4-dihydroxytoluene in acetonitrile (AN). Tyrosinase, a hydrophilic biofunctional material, was immobilized in the thin PAA membrane, which adhered to the platinum-disk electrode and was stable in AN. The enzymatic activity of tyrosinase in the PAA membrane to the above substrates in AN was confirmed by cyclic voltammetry and amperometry. The apparent maximum velocities (Vmaxapp) and the apparent Michaelis constants (Kmapp) were determined from the amperometric results; the apparent turnover numbers were also determined. The reduction potentials of the substrates were reported vs. the cathodic peak potential of ferrocene in AN to improve the reliability of the potential data and to make possible a comparison of the potentials in different solvents. The electrochemical system discussed in this report can be used for tracing enzymatic reactions with substrates dissolving in aprotic dipolar solvents and for investigating solvent effects on enzymatic activities.     

Synthesis and antioxidant activity of sterically hindered bis-pyrocatechol thioethers

A reaction of 3,5-di-tert-butyl-o-benzoquinone with 1,2- and 1,6-dithiols was used to obtain the corresponding bis-pyrocatechol thioethers; a comparative evaluation of their antioxidant activity was carried out. The synthesized thioethers, 2-(4,6-di-tert-butyl-2,3-dihydroxyphenylsulfanyl)acetic acid, and 3,5-di-tert-butylpyrocatechol were studied in the reaction with diphenylpicrylhydrazyl radical. The influence of these compounds on the autooxidation process of oleic (cis-octadec-9-enoic) acid was studied. The antioxidant activity of bis-pyrocatechol thioethers was manifested in the reaction with diphenylpicrylhydrazyl radical in the process of autooxidation of oleic acid, which was confirmed by the experimental EC₅₀ values, the data on the number of transformed molecules of stable radical ( ⁿ DPPH), and the relative content of oleic acid hydroperoxides. Bis-pyrocatechol thioethers were found to exhibit the inhibitory activity in the course of oxidation of glutathione induced by 2,2’-azobis(2-amidinopropane) dihydrochloride.     

Electrochemical reduction of gaseous CO2 with a catechol and polyethyleneimine co-deposited polypropylene membrane

A novel solid polymer electrolyte was developed by co-deposition of catechol (CCh) and polyethyleneimine (PEI) on a polypropylene membrane for electrochemical reduction of CO₂ (ERC) in gas phase. ERC performance was both investigated in a gas-gas mode and a gas-liquid mode. The maximum CO production rate was 121 μmol/h and the faradaic efficiency was 51% in the gas-liquid mode, which were much higher than those obtained with AM-7001 under the same condition. The high loading rate of quaternary ammonium ions on the membrane and the large surface area provided by the porous nano-structure of the membrane contribute to the high ERC efficiency. Furthermore, the cost of the CCh/PEI-Q membrane was much lower than commercial Nafion membranes, endowing this novel composite SPE with great potential in industrial application.     

Antioxidant and prooxidant activity of spent coffee extracts by isothermal calorimetry

Journal of Thermal Analysis and Calorimetry - This work aims to determine the antioxidant and prooxidant activity of spent coffee extracts obtained with (1) a low-pressure (LP) extraction with...     

Electrochemical sensing of concanavalin A using a non-ionic surfactant with a maltose moiety

To electrochemically detect concanavalin A (ConA), a new method was developed using mixed micelles between a non-ionic surfactant with a maltose moiety and electroactive daunomycin. The surfactants, in which the length of the alkyl chain was different, were n-decyl-β-d-maltoside, n-dodecyl-β-d-maltoside, and n-tetradecyl-β-d-maltoside. The measurement principle was due to the micelle breakdown caused by the binding between the ConA and maltose moieties. When ConA was combined with maltose moieties at a concentration of surfactant that was near the critical micelle concentration, the daunomycin that formed the micelles was moved to a solution from the micelles. As a result, the peak current of daunomycin increased as the concentration of ConA was increased. The mechanism was proposed using voltammetry, spectrometry, and gel filtration. The linear range using n-tetradecyl-β-d-maltoside was 2.0 × 10⁻⁹ to 8.0 × 10⁻⁸ M of ConA, and it was the most sensitive in the presence of the three surfactants. To examine whether selective binding took place, measurements with several proteins were carried out. The electrode responses of daunomycin were not influenced by the presence of 5.0 × 10⁻⁶ M protein. Furthermore, this method could be applied to the determination of ConA in a serum, and to the measurement of sugar chains that can be combined with ConA on the cell surface.     

Electrochemical sensing of anions by redox-active receptors built on the ferrocenyl cyclam framework

A range of ferrocenyl derivatives, L₁–L₃ and L₁Cu, has been prepared and their electrochemical recognition properties in organic solvents have been studied. These compounds are built on the same cyclam framework (ferrocenyl trans di-substitued cyclam), but they differ by the nature of their anions binding sites. While L₁ and its corresponding N-methylated L₂ derivative can interact with anionic species via H-bonding, strong electrostatic and hard acid–hard base interactions with anionic species are mainly involved in the ammonium derivative L₃ and the copper(II) complex L₁Cu, respectively. Significant CV perturbations in the characteristic potential of the Fc/Fc⁺ subunit in the presence of anions were found with L₁ and L₃. Selectivity of the electrochemical process is likely to be based on the formation of multiple H-bonds between the secondary amines of L₁ and the phosphate anions (both H-donor and acceptor) when the topology of the ammonium derivatives, L₃, governs mainly the anion complexation. Clear cyclic voltammetric features, such as a well-defined two-wave behavior allowing an accurate amperometric titration, require that the redox receptor contain an appropriate binding site and the ferrocene group in close proximity. Lewis acid–base interactions were shown to influence more deeply the electroactivity of Lewis acid center, namely the copper center in L₁Cu, than that of the ferrocenyl redox probe that is not directly connected to the associated anion. However, the precipitation of the host structure (e.g., L₃ or L₁Cu) in the presence of oxo-anions shows that a compromise has to be found between the establishment of strong interactions and the formation of soluble ion-pairs based complexes.     

Synthesis and antimicrobial activity of novel spirocompounds with pyrazolone and pyrazolthione moiety

The paper focuses on the utility of 2‐pyrazoline‐5‐ones and 2‐pyrazoline‐5‐thiones as active Michael donors for the synthesis of novel spirocyclohexanone derivatives. The sulphur containing compounds when screened for antimicrobial activity showed promising inhibition of S. Typhi, S Aures and E Coli bacteria.     

Electrochemical investigation of a photochromic spiropyran containing a pyrrolidinofullerene moiety

Reversible transformations of a hybrid molecule based on [60]fullerene and a spiropyran moiety under conditions of combined photo- and electrochemical exposure were found. It has been established that the electrochemical oxidation of the UV-photoinduced colored form of the hybrid spiropyran in solution significantly accelerates the discoloration process and does not affect the fullerene part of the hybrid molecule. The research results are promising for designing a photo-electrochromic device that modulates electromagnetic radiation in the visible range of the spectrum.     

Electrochemical behavior of zopiclone

The electrochemical properties of zopiclone, an anxiolytic and hypnotic drug, have been investigated by different techniques. The compound is reduced in two 2-electron steps in the pH range 0-12. The first step, which corresponds to the reduction of the pyrazine ring, is reversible in acidic and neutral solutions. Strong adsorption phenomena accompany the reduction process in acidic and neutral media. Zopiclone can be quantitatively measured over the entire pH range using DC polarography. However, the use of differential pulse and square-wave modes for quantitative measurements is more limited due to a slope modification in the current-concentration relationship. Adsorptive stripping voltammetry can be applied to the determination of low levels of the drug at pH 9, but only short deposition times may be used because large amounts of material accumulated under stirring conditions due to fast adsorption kinetics are rapidly released from the electrode surface. Detection limits are 1 x 10(-7)M and 2 x 10(-10)M for polarography and adsorptive stripping voltammetry, respectively. Only the first wave is of analytical interest for both techniques.