Experimental and theoretical studies of electrochemical characteristics of 3,4-dihydroxyphenylacetic acid (DOPAC)

The electrochemical behavior of 3,4-dihydroxyphenylacetic acid (DOPAC) in aqueous solutions with different pHs and DOPAC concentrations was studied by cyclic voltammetry at various potential scan rates. The electro-oxidation of DOPAC involves a transfer of two electrons and two protons in solutions of pH < 8.0 and a transfer of two electrons and one proton in solutions of pH > 8.0, in agreement with the one-step two-electron mechanism. The cyclic voltammetry indicated that the process of electro-oxidation of DOPAC follows an E_rC_i mechanism. The standard redox potential, E⁰′, two-proton-two-electron and one-proton-two-electron processes of DOPAC were determined as 0.585 and 0.357 V versus saturated calomel electrode (SCE), respectively. The acidic dissociation constant of DOPAC was also obtained. Also, the diffusion coefficient of DOPAC was calculated as 9.2 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometric results. The standard reduction potentials and the second acidic constant of DOPAC have been also calculated using standard ab initio calculations at the G3 level of theory in conjunction with a continuum solvation model. The theoretical values are in good agreement with experiment.     

First RAFT polymerization of captodative 2-acetamidoacrylic acid (AAA) monomer: An experimental and theoretical study

A capto-dative monomer, 2-acetamidoacrylic acid (AAA), was homopolymerized through RAFT polymerization method using 2-(2-cyanopropanyl dithiobenzoate) (CPDB) as a chain transfer agent and AIBN free radical initiator in DMF at 70 °C. DFT calculations were performed in the selection of the CTA for this unique monomer as well as to elucidate the influence of cd-stabilized growing radical on the kinetic parameters in comparison to methacrylic acid (MAA) and N-(prop-1-en-2-yl)acetamide (NPAA), which represent the captive and dative groups of AAA, respectively. K_eq for these three monomers is in the order of AAA < MAA < NPAA. While k_β > k_−add for NPAA and MAA, for AAA k_−add is about four orders of magnitude larger than k_β. This is the major disadvantage in the RAFT process of AAA using CPDB. Yet, poly(AAA) could be achieved with PDI as low as 1.49. Molecular weight of the polymer can be tuned by the monomer/AIBN ratio. First block copolymers of AAA with MAA and MMA using poly(AAA) as a macro-CTA were also synthesized, indicating the presence of active chain ends.     

Electrochemistry, spectroelectrochemistry and electrochemical polymerization of titanylphthalocyanines

Detailed electrochemical characterization of tetrakis(2-dimethylaminoethylsulfanyl phthalocyaninato) oxotitanium(IV) and octakis(2-dimethylaminoethylsulfanyl phthalocyaninato) oxotitanium(IV) derivatives has been carried out by the cyclic voltammetry, differential pulse voltammetry, controlled potential chronocoulometry and spectroelectrochemical measurements. Cyclic and differential pulse voltammograms of both complexes are similar, with two metal-based and one ligand-based reduction couples having diffusion controlled reversible one-electron transfer character. Both complexes are polymerized on the working electrode electrochemically during the positive potential sweeps. Spectroelectrochemical measurements confirm the metal and ligand-based assignments of the redox couples.     

Evaluation of chlorogenic acid and its metabolites as potential antioxidants for fish oils

The antioxidant effects on cod liver oil (CLO) of chlorogenic acid (CGA) and its metabolites, caffeic acid (CA) and quinic acid (QA), were investigated. All three chemicals were separately added to CLO at a concentration range of 0.001–0.080 wt‐% and tested by Rancimat. CA was the best antioxidant; its antioxidant effect was directly proportional to the dose added, but only within the concentration range of 0.005–0.050 wt‐%. QA did not show any effect on CLO oxidation, while CGA revealed itself as a weak antioxidant. Cytotoxicity was also evaluated by using murine 3T6 fibroblasts treated for 24 h with CGA, CA and QA at a concentration range of 0.1–5.0 mM. QA did not have an influence on cell proliferation, while CGA and CA showed a significant anti‐proliferative activity already at a concentration of 0.1 mM. Finally, compounds similar to the standard 8‐iso prostaglandin F_2α, called CLO‐“isoprostanes”‐like compounds, were isolated. At high temperature (100 and 110 °C) CLO‐“isoprostanes‐like” compounds did not show a relevant pro‐oxidant action on the refined olive oil to which they were added in variable amounts. On the contrary, the CLO‐“isoprostanes”‐like compounds significantly decreased the antioxidant effectiveness of CA. Indeed, at a CLO‐“isoprostanes‐like” compound dose of 300 µg, the antioxidant effectiveness of CA was halved.     

Electrooxidation of 4-methylcatechol in the presence of barbituric acid derivatives

Electrooxidation of 4-methylcatechol (1) in the presence of 1,3-dimethylbarbituric acid (2a) and 1,3-diethylthiobarbituric acid (2b) as nucleophiles has been studied in detail by cyclic voltammetry and controlled-potential coulometry. The results indicate that 1 can be oxidized to its related o-benzoquinone (1a) and without conversion to its quinone methide tautomeric form, via an ECEC mechanism pathway, is converted to barbiturate derivatives (5a-b). The electrochemical synthesis of 5a-b have been successfully performed in one-pot in an undivided cell.     

Electrochemical mechanism and kinetics studies of haloperidol and its assay in commercial formulations

The kinetics and mechanism for electrochemical reduction of haloperidol, a psychotherapeutic drug used in the treatment of schizophrenia, were studied using square wave and cyclic voltammetries allied to a hanging mercury drop electrode. The experimental and voltammetric parameters were optimized at 0.04 mol L⁻¹ Brinton–Robinson buffer (pH 10), with a pulse potential frequency of 100 s⁻¹, a pulse amplitude of 30 mV and scan increment of 2 mV. Two well-defined peaks were observed, which exhibited properties of fast electron transfer with a strong adsorption process of reactants and products on the electrode surface. The first peak was related to a fast and reversible anion-radical formation originating from the reduction of the carbonyl group, and the second was related to the irreversible reduction of the anion-radical previously formed. Analytical parameters such as: linearity range, equation of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday were compared to similar results obtained by use of the UV–vis spectrophotometry technique, and the analytical results obtained in commercial formulations show that the voltammetric procedure using a hanging mercury drop electrode is suitable for analyzing haloperidol in complex commercial formulation samples.     

几种芳香化合物电化学性质的研究

采用循环伏安法考察了苯胺在铂电极上不同浓度、pH值和不同扫描速率等条件下的电化学反应特性。结果表明:在中性条件下,苯胺未出现明显的氧化还原峰,氯苯、苯甲酸分别出现了2个氧化峰和1个还原峰;随着硫酸浓度的增大,氯苯和苯甲酸峰电流密度呈减小趋势,而苯胺峰电流密度增大,这可能与氨基、氯、羧基的Hammet常数和溶液的pH值有关,Hammet常数越小易于发生亲电攻击;苯胺的氧化峰和还原峰相比大约为1,接近于可逆反应,苯胺的可逆性最强。     

Medium effects on the electro-deposition of MnO2 on glassy carbon electrode: A comparative study in alkane, perfluoro alkane carboxylic acids and methanesulphonic acid

Voltammetric studies of Mn(II) were carried out in acetic acid (AA), trifluoroacetic acid (TFA), butyric acid (BA), perfluorobutyric acid (PFBA) and methanesulphonic acid (MSA) media. Influence of anodic limit and the nature of acids were investigated. Oxidation of Mn(II) shows two anodic peaks in weak acids namely acetic acid and butyric acid media due to the formation of insoluble Mn(III) and Mn(IV) species. Reduction of these species were also observed as two peaks in the cathodic region. Formation and reduction of solid oxide phases are the dominant electrode processes in such weak acid media. In strong acids like MSA and TFA media sharp anodic and cathodic peaks were obtained due to the formation and reduction of stable soluble Mn(III) species. SEM studies reveal the formation of thicker oxide phases in weak acid media and much thinner oxide layers in strong acid media. γ-MnO₂ phase was formed from AA and TFA while -MnO₂ phase was formed from BA and PFBA, suggesting a relationship between phase structure and anionic size.     

Polyaniline fibres as electrodes.: Electrochemical characterisation in acid solutions

Polyaniline fibre microelectrodes prepared from a doped solution of polyaniline protonated with 2-acrylamido-2-methyl-1-propanesulphonic acid in dichloracetic acid were characterized electrochemically for the first time. Low scan rate cyclic voltammetry was used for characterisation in different acid electrolyte solutions, hydrochloric, nitric, perchloric, sulphuric and phosphoric, at low pH values with varying positive potential limits. Electrochemical impedance spectroscopy was also utilised. The electrochemical behaviour of polyaniline (PANI) fibres was found to be similar to that of PANI films obtained by electropolymerisation on metallic electrode substrates. The conduction potential window was found to be from +0.20 to +0.60 V versus SCE, with small variations in the different acid solutions as well as with pH. The standard electrochemical redox couple hexacyanoferrate(III), was found to behave quasi-reversibly in the conduction potential region and rate constants were evaluated.     

The electrochemical synthesis of polyaniline/polysulfone composite films and electrocatalytic activity for ascorbic acid oxidation

Polyaniline (PANI)/polysulfone (PSF) composite films with asymmetric porous structure were successfully prepared by electropolymerization. The back face (in contact with the electrode) of the freestanding composite film is green while the outer face is white. The chemical component and the morphology of the surfaces were characterized by FTIR spectra and scanning electron microscopy, respectively. It was shown that replicate films gave reproducible voltammetry in 0.5 M H₂SO₄. The influence of the electrolyte and the acidic concentration on the redox peak currents of polyaniline were investigated in detail. The composite film electrode showed good electrocatalytic activity for ascorbic acid, which the anodic overpotential was evidently reduced compared with that obtained at bare Pt electrode. The diffusion coefficient of ascorbic acid was 1.38 × 10⁻⁶ cm² s⁻¹.     

Electrochemical oxidation of acetaminophen in aqueous solutions: Kinetic evaluation of hydrolysis, hydroxylation and dimerization processes

Electrochemical oxidation of acetaminophen (paracetamol) has been studied in various pHs using cyclic voltammetry and controlled-potential coulometry. The results indicate that electrochemically generated N-acetyl-p-benzoquinone-imine (NAPQI) participates in different type reactions based on solution's pH. It is hydrolyzed in strong acidic media and hydroxylated in strong alkaline media and also, it is dimerized in intermediate pHs. Furthermore, in this work, a simple method for electrochemical synthesis of acetaminophen's dimer is described. In addition, in various pHs, based on related mechanism, the observed homogeneous rate constants (k_obs) of hydrolysis, hydroxylation and dimerization reactions were estimated by comparing the experimental cyclic voltammetric responses with the digital-simulated results. The most amounts of k_obs are calculated in pHs less than 2 and more than 9. In this study, the least observed homogeneous rate constant (k_obs) belongs to pHs 5.0 and 9.0.     

Potential control characteristics of short-chain thiols of thioctic acid and mercaptohexanol self-assembled on gold

In this article we systematically investigated self-assembly of short-chain thiols of thioctic acid (TA) and mercaptohexanol (MCH) on gold under potential control, E_dc (−0.4, +0.4 and +0.7 V) and compared the results obtained with open circuit potential (E_OCP). Effect of E_dc on thiol self-asembly was inspected based on the changes in electrochemical parameters including interfacial capacitance (C), phase angle (Φ_1Hz), current density difference (Δi), charge transfer resistance (R_ct) through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Experimental results showed that E_dc could not obtain stable short-chain self-assembled monolayers (SAMs) (TA and MCH) in a short time. Both TA and MCH had slow self-assembly dynamics and needed a long time (> 24 h) to achieve adsorption equilibrium. Furthermore, the negative potential E_dc (−0.4 V) did not facilitate the ordering of SAMs. The ordering of TA-SAMs was found to be the best when assembled under E_dc (+0.4 V), whereas that of MCH-SAMs was almost the same when assembled under either E_OCP or E_dc (+0.4, +0.7 V). We considered that permeation of ions and water molecules perhaps dominated the slow self-assembly dynamics of short-chain thiols (TA and MCH) under E_dc and mutual interaction between adjacent chains of thiols played an important role in the ordering of SAMs.     

Electrochemical Oxidation of Phenol on Metal‐Impregnated Zeolite Electrodes

Nanodispersed metallic clusters of platinum, silver and cobalt were incorporated into NaX zeolite cavities by impregnation with acetone solution of corresponding acetylacetonates and solvent evaporation followed by acetylacetonate thermal decomposition. The mixture of modified zeolites and 10 wt % of carbon black, in the form of a thin layer, was pasted onto a glassy carbon surface by Nafion. With such electrode materials, the phenol oxidation in neutral, alkaline and acid solution was studied by cyclovoltammetry. Deactivation of all electrodes in both neutral and alkaline medium was observed, indicating that polymerization reaction might be the main reaction pathway of phenol at higher pH values. Formation of quinine‐type structures was obtained during electro‐oxidation at lower pH values, being more significant in acidic solutions.     

Electrochemistry and spectro-electrochemistry of dithizonatophenylmercury(II)

The reactions between dithizone (H₂Dz, (1)) or potassium dithizonate (K⁺HDz⁻, (2)) and phenylmercury(II) chloride gives PhHg(HDz), (3). Complex (3) is photochromic. In dichloromethane, the blue photo-exited state of (3) exhibits a first order relaxation process to regenerate the orange ground state with rate constant 0.00053 s⁻¹. The half life of this relaxation is ca. 1300 s. Electrochemically, on cyclic voltammetry time scale, the oxidations of (1) and (3) are different. A comparative voltammetric and spectro-electrochemical study of (1) and (3) in CH₂Cl₂ containing 0.1 mol dm⁻³ [N(ⁿBu)₄][B(C₆F₅)₄] revealed that the mercapto group of (1) can be oxidised in two one-electron transfer steps. A disulphide is first produced and then in a second oxidation step, HDz⁺ is formed. In contrast, complex (3) shows only one ligand-based oxidation step. Upon complexation with phenylmercury the free mercaptan group of (1) becomes a stable “metal thioether”, Hg–S–C, which effectively prevents disulphide formation in (3) upon electrochemical oxidation. Both (1) and (3) shows two reduction steps. The electrochemical fingerprint of blue photo-excited (3) is identical to that of the orange ground state as no new functional groups are introduced upon irradiation; only bond rotation occurs. The different electronic spectra for each of the redox states of (3), obtained from spectro-electrochemical measurements, revealed that only the (3)/(3⁻) couple exhibits electrochromic properties.     

Electrochemical chlorination of azulene derivatives: Insight into the mechanism of anodic oxidative chlorination

The cyclic voltammetry behavior of a series of five 1-substituted azulenes has been investigated as well as the electrochemical chlorination of these compounds. In the case of azulene compounds containing electron withdrawing groups which have higher oxidation potentials than that of the chloride ion, the electrochemical chlorination led usually to 3-chloro derivatives. The electrochemical chlorination fails for azulenes with lower oxidation potentials. Additionally some polyhalogenated compounds were obtained by controlled potential electrolyses. The paper also discusses the reaction mechanism of the electrochemical halogenation of 1-substituted azulenes.     

Electrochemical properties of benzylmercapto and dodecylmercapto tetra substituted nickel phthalocyanine complexes: Electrocatalytic oxidation of nitrite

Nickel tetrakis(benzylmercapto)phthalocyanine (NiTBMPc) and nickel tetrakis(dodecylmercapto)phthalocyanine (NiTDMPc) complexes were synthesized and their spectral and electrochemical properties reported. The CV showed four or five redox processes for NiTBMPc and NiTDMPc, respectively. For the first time, spectroelectrochemistry gave evidence for the formation of Ni^II/Ni^I process in a NiPc complex. The rest of the processes were ring based. The NiTBMPc complex was successfully deposited on both gold and glassy carbon electrodes by electropolymerisation while NiTDMPc complex was deposited on gold electrode only. The films were electro-transformed in aqueous 0.1 M NaOH solution to the O–Ni–O oxo bridged form. The modified electrodes were characterized using electrochemical impedance spectroscopy and the results showed typical behavior for modified electrodes. Electrodes with poly-Ni(OH)Pcs films exhibited higher charge transfer resistance values, R_p than their corresponding poly-NiPcs films counterparts. All the modified electrodes showed improved catalytic activities than the unmodified electrodes towards nitrite ions electrooxidation. Better catalytic activities were observed for the modified electrodes when they were transformed to O–Ni–O oxo bridge form. All the modified electrodes exhibited high resistance to electrode surface passivation.     

Platinum modification of gold and electrocatalytic oxidation of ethylene glycol on Pt-modified Au electrodes

The surface modification of gold electrodes with platinum and the electrocatalytic oxidation of ethylene glycol on Pt-modified Au electrodes are investigated by cyclic voltammetry. Platinum modification is performed by the electrochemical deposition of platinum on polycrystalline gold electrodes, and the Pt-modified Au electrodes with different amount of the deposited platinum are used for the ethylene glycol oxidation in alkaline and acidic solutions. It is shown that oxidation potential for the ethylene glycol oxidation on the Pt-modified Au electrodes shifts significantly negative compared with that on Au electrodes, nearly same oxidation potentials as that on Pt electrodes are observed, and peak current density of the ethylene glycol oxidation is dependent on the amounts of the deposited platinum on gold surface, much higher peak current densities than that on Au and Pt electrodes can be obtained. The low oxidation potential and high peak current density indicate the enhanced reactivity of Au electrodes by the platinum modification. The characteristics of the Pt-modified Au electrodes are found to be similar to that of Pt electrodes, and the reactivity of the Pt-modified Au electrodes is mainly attributed to the deposited platinum.     

Electrochemical and DFT-studies of substituted thiophenes

UV-vis absorption spectra and cyclic voltammograms of a selection of substituted thiophenes and their oligomers carrying trifluoracetyl acetone functional groups have been obtained. A comparison with calculated values of HOMO-LUMO energies (the former corresponding to the ionization potentials E_i) shows strong correlations between calculated and experimentally obtained data; they are in close agreement with estimates in terms of electron-donating and -withdrawing effects from an empirical point of view.     

Electrochemical quartz crystal nanobalance (EQCN) studies of the adsorption behaviour of an enzyme, mandelate racemase, and its substrate, mandelic acid, on Pt

The adsorption behaviour of the enzyme, mandelate racemase (MR), and its substrate, (S)-mandelic acid (MA), was studied at a polycrystalline Pt surface in pH 7.4 phosphate buffer at 294 K using the electrochemical quartz crystal nanobalance (EQCN) technique of simultaneous cyclic voltammetry (CV) and frequency measurements. It was shown that the EQCN frequency measurements did not directly monitor the molar mass of the adsorbed protein at anodic potentials, but instead measured changes in the surface oxide in the absence and presence of adsorbed protein. However, at a potential characteristic of the double layer for platinum, EQCN frequency measurements gave a measure of the extent of solvent displacement by the adsorbed protein. The adsorption process was modelled using the Langmuir adsorption isotherm. The values for the Gibbs energy of adsorption, ΔG_ADS, obtained with these EQCN frequency measurements gave excellent agreement within experimental uncertainty with those obtained from the simultaneous CV measurements for both the enzyme and substrate, and showed the enzyme to have a greater affinity for the surface than the substrate molecule. The maximum surface concentrations from CV and EQCN frequency measurements gave excellent agreement for the two techniques and showed MA to be adsorbed in a tilted orientation with monolayer coverage. On the other hand, the surface concentrations showed the presence of ∼2.5 monolayers of enzyme from charge transfer CV measurements, while the frequency results showed the presence of a densely packed monolayer from the “footprint” of solvent displacement by the adsorbed enzyme molecules on the electrode surface. The two techniques provide valuable complementary information on the interfacial behaviour of molecules.