Synthesis of 3-O-methylgallic acid a powerful antioxidant by electrochemical conversion of syringic acid.

BACKGROUND: A kinetic study of the electrochemical oxidation of syringic acid (3,5-dimethoxy-4-hydroxybenzoic acid) by cyclic voltammetry at treated gold disk was combined with results of electrolyses at Ta/PbO2 anode in order to convert it into potentially high-added-value product. METHODS: The electrochemical oxidation of syringic acid was carried out in order to convert this compound to 3-O-methylgallic acid. This latter was identified by mass spectrophotometry using LC-MS/MS apparatus. The 3-O-methylgallic acid synthesis was controlled by cyclic volammetry, Ortho-diphenolicdeterminations and DPPH radical-scavenging activity. RESULTS: The proposed mechanism is based on the hypothesis of a bielectronic discharge of syringic acid molecule under free and adsorbed form involving two intermediate cation mesomers. Hydrolysis of the more stable of this last one leads to the formation of the 3,4-dihydroxy-5-methoxybenzoic acid (3-O-methylgallic acid) as a major product. The latter aromatic compound was synthesized by anodic oxidation of syringic acid at PbO2 electrode. The cyclic voltammogram of the electrolysis bath of syringic acid shows that the anodic peak potential of 3-O-methylgallic acid was lower (Epa=128mV) than that of SA (Epa=320mV). And the strongest antiradical activity was detected when the 3-O-methylgallic acid concentration was higher". CONCLUSION: The electrochemical oxidation using PbO2 anode is a rapid, simple and efficient method tool for a conversion of SA into 3-O-methylgallic acid, a potent antioxidant derivative GENERAL SIGNIFICANCE: The electrochemical process consists in a simple transformation of the syringic acid into 3-O-methylgallic acid having a better antioxidant capacity. This result has been justified by cyclic voltametry which shows that anodic peak of 3-O-methylgallic acid is reversible. Furthermore, its potential is lower than that of the irreversible anodic peak of syringic acid to 3-O-methylgallic acid.

Degradation of 4-chloroguaiacol by dark Fenton and solar photo-Fenton advanced oxidation processes.

This paper evaluates the dark Fenton and the solar photo-Fenton advanced oxidation processes for the treatment of solutions containing 4-chloroguaiacol (4-CG). The 4-CG was chosen as a model compound found in pulp and paper wastewater formed in the bleaching process in the pulp industry. The effects of operating parameters, including reaction time, hydrogen peroxide-to-ferrous iron molar ratio (H2O2/Fe2+), initial chemical oxygen demand (COD), pH value, and temperature, on 4-CG degradation efficiency using the solar photo-Fenton process were investigated. It was demonstrated that both processes could effectively degrade 4-CG in water and followed first-order kinetics. The degradation rate in solar photo-Fenton oxidation was much faster than that of the dark reaction. The 4-CG degradation depends on its concentration in the solution. The degradation efficiency decreases when the concentration of the 4-CG increases. Under the conditions of pH 3, H2O2/Fe2+ molar ratio 2, H2O2 16 mmol x L(-1), Fe2+ 8 mmol x L(-1), initial COD 640 mg x L(-1), reaction time approximately 24 minutes, and temperature 25 degrees C, the 4-CG and COD percent removal were greater than 80 and 89%, respectively.

Chemical composition and direct electrochemical oxidation of table olive processing wastewater using high oxidation power anodes.

Table olive processing wastewater (TOW) is a notoriously polluting due to its high organic and phenol content. To reduce them, an electrochemical process has been studied for the treatment of this effluent. Experiments were performed with a cell equipped with lead dioxide (PbO2) or boron-doped diamond (BDD) as anode and platinum as cathode, where Table Olive Wastewater (TOW) were destroyed by hydroxyl radicals formed at the anode surface from water oxidation. The comparative study of both systems shows the performance of the BDD anode compared to PbO2, explained by the large amounts of hydroxyl radicals generated effective at BDD anode and its synthesis characteristics. Using LC/MS analysis, it was possible to determine hydroxytyrosol, as major phenolic compounds, in table olive processing wastewater and its concentration reach 890 mg L-1. A possible reaction mechanism oxidation for hydroxytyrosol was proposed. The kinetics decays for hydroxytyrosol degradation on PbO2 anode follows a pseudo-first order reaction with a rate constant 0.9 h-1 for japp value 20 mA cm-2.

Boron doped diamond sensor for sensitive determination of metronidazole: Mechanistic and analytical study by cyclic voltammetry and square wave voltammetry.

The performance of boron-doped diamond (BDD) electrode for the detection of metronidazole (MTZ) as the most important drug of the group of 5-nitroimidazole was proven using cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. A comparison study between BDD, glassy carbon and silver electrodes on the electrochemical response was carried out. The process is pH-dependent. In neutral and alkaline media, one irreversible reduction peak related to the hydroxylamine derivative formation was registered, involving a total of four electrons. In acidic medium, a prepeak appears probably related to the adsorption affinity of hydroxylamine at the electrode surface. The BDD electrode showed higher sensitivity and reproducibility analytical response, compared with the other electrodes. The higher reduction peak current was registered at pH11. Under optimal conditions, a linear analytical curve was obtained for the MTZ concentration in the range of 0.2-4.2µmolL(-1), with a detection limit of 0.065µmolL(-1).

Effect of olive storage conditions on Chemlali olive oil quality and the effective role of fatty acids alkyl esters in checking olive oils authenticity.

The present paper accounts for the study of the storage of Chemlali olive fruits at two conditions of limited aerobiosis: in closed plastic bags and in open perforated plastic boxes for different periods before oil extraction. The ultimate objective is to investigate the effect of the container type of the postharvest fruit storage on the deterioration of the olive oil quality. The results have shown that the oil quality of Chemlali olives deteriorated more rapidly during fruit storage in closed plastic bags than in perforated plastic boxes. Therefore, the use of perforated plastic boxes is recommended for keeping the olives for longer periods of storage. The repeated measures analysis of variance of all parameters analyzed indicated that the olive oil quality is mainly affected by the olives storage conditions (containers type and storage periods). Finally, blends of extra-virgin olive oil and mildly deodorized low-quality olive oils can be detected by their alkyl esters concentrations.

Degradation of tyrosol by a novel electro-Fenton process using pyrite as heterogeneous source of iron catalyst.

Tyrosol (TY) is one of the most abundant phenolic components of olive oil mill wastewaters. Here, the degradation of synthetic aqueous solutions of 0.30 mM TY was studied by a novel heterogeneous electro-Fenton (EF) process, so-called EF-pyrite, in which pyrite powder was the source of Fe(2+) catalyst instead of a soluble iron salt used in classical EF. Experiments were performed with a cell equipped with a boron-doped diamond anode and a carbon-felt cathode, where TY and its products were destroyed by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between Fe(2+) and H2O2 generated at the cathode. Addition of 1.0 g L(-1) pyrite provided an easily adjustable pH to 3.0 and an appropriate 0.20 mM Fe(2+) to optimize the EF-pyrite treatment. The effect of current on mineralization rate, mineralization current efficiency and specific energy consumption was examined under comparable EF and EF-pyrite conditions. The performance of EF-pyrite was 8.6% superior at 50 mA due to self-regulation of soluble Fe(2+) by pyrite. The TY decay in this process followed a pseudo-first-order kinetics. The absolute rate constant for TY hydroxylation was 3.57 × 10(9) M(-1) s(-1), as determined by the competition kinetics method. Aromatic products like 3,4-dihydroxyphenylethanol, 4-hydroxyphenylacetic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and catechol, as well as o-benzoquinone, were identified by GC-MS and reversed-phase HPLC. Short-chain aliphatic carboxylic acids like maleic, glycolic, acetic, oxalic and formic were quantified by ion-exclusion HPLC. Oxalic acid was the major and most persistent product found. Based on detected intermediates, a plausible mineralization pathway for TY by EF-pyrite was proposed.

Phenolic profile characterization of Chemlali olive stones by liquid chromatography-ion trap mass spectrometry.

Aqueous methanol extracts of Chemlali olive stones were analyzed by reverse phase high-performance liquid chromatography (HPLC) with diode array detection and mass spectrometry [LC-MS/MS]. Oleoside, oleoside 11-methyl ester, nuezhenide, oleoside 11-methyloleoside, nuezhenide 11-methyloleoside, oleuropein, and glycosides of tryosol and hydroxytyrosol glycosides were identified in stones of Chemali olives. The antioxidant activity observed for the extract of the olive stones (IC50 = 13.84 µg/mL, TEAC = 0.436 mM) may be due to the high content of phenolic compounds, of which the main compounds are nuezhenide (325.78 mg/100g), methoxy derivative of nuezhenide (132.46 mg/100g), and nuezhenide-11-methyloleoside (82.91 mg/100g). These results suggest the use of olive stones as sources of natural antioxidants.

Detection of Chemlali extra-virgin olive oil adulteration mixed with soybean oil, corn oil, and sunflower oil by using GC and HPLC.

Fatty acid composition as an indicator of purity suggests that linolenic acid content could be used as a parameter for the detection of extra/virgin olive oil fraud with 5% of soybean oil. The adulteration could also be detected by the increase of the trans-fatty acid contents with 3% of soybean oil, 2% of corn oil, and 4% of sunflower oil. The use of the ΔECN42 proved to be effective in Chemlali extra-virgin olive oil adulteration even at low levels: 1% of sunflower oil, 3% of soybean oil, and 3% of corn oil. The sterol profile is almost decisive in clarifying the adulteration of olive oils with other cheaper ones: 1% of sunflower oil could be detected by the increase of Δ7-stigmastenol and 4% of corn oil by the increase of campesterol. Linear discriminant analysis could represent a powerful tool for faster and cheaper evaluation of extra-virgin olive oil adulteration.

Application of electrochemical technology for removing petroleum hydrocarbons from produced water using lead dioxide and boron-doped diamond electrodes.

Although diverse methods exist for treating polluted water, the most promising and innovating technology is the electrochemical remediation process. This paper presents the anodic oxidation of real produced water (PW), generated by the petroleum exploration of the Petrobras plant-Tunisia. Experiments were conducted at different current densities (30, 50 and 100 mA cm(-2)) using the lead dioxide supported on tantalum (Ta/PbO2) and boron-doped diamond (BDD) anodes in an electrolytic batch cell. The electrolytic process was monitored by the chemical oxygen demand (COD) and the residual total petroleum hydrocarbon [TPH] in order to know the feasibility of electrochemical treatment. The characterization and quantification of petroleum wastewater components were performed by gas chromatography mass spectrometry. The COD removal was approximately 85% and 96% using PbO2 and BDD reached after 11 and 7h, respectively. Compared with PbO2, the BDD anode showed a better performance to remove petroleum hydrocarbons compounds from produced water. It provided a higher oxidation rate and it consumed lower energy. However, the energy consumption and process time make useless anodic oxidation for the complete elimination of pollutants from PW. Cytotoxicity has shown that electrochemical oxidation using BDD could be efficiently used to reduce more than 90% of hydrocarbons compounds. All results suggest that electrochemical oxidation could be an effective approach to treat highly concentrated organic pollutants present in the industrial petrochemical wastewater and significantly reduce the cost and time of treatment.

Effect of processing systems on the quality and stability of Chemlali olive oils.

The present work has been carried out to ascertain the influence of different processing systems employed in olive process on the chemical composition, quality and stability of three Chemlali olive oils. Among these oils, two were classified as extra-virgin olive oils and the third named repassed olive oil was classified as an ordinary virgin olive oil. The analysis of the effect of the processing (two- and three-phases) on the analytical determinations values, revealed statistically significant differences (p<0.05) in some parameters, mainly in oxidative stability, antioxidant activity, total waxes, total phenols, o-diphenols and α-tocopherol contents as well as phenolic composition. The phenolic composition values were higher in the extra-virgin olive oil obtained from the two-phase system than in that obtained from the three-phase processing because it does not require the addition of water to the olive paste. Nevertheless, they were lower in the ordinary virgin olive oil (repassed olive oil) which was obtained by introducing hot water to the wet residues into the centrifugation processing at two-phases, than those in the extra-virgin olive oils obtained from the two- and three-phase processing.

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes.

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton's reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H(2)O(2) dosing rate, initial concentration of Fe(2+), and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H(2)O(2). Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H(2)O(2) 40% lower than that used in the Fenton process to remove 90% of COD.

Electrochemical degradation of waters containing O-toluidine on PbO2 and BDD anodes.

Electrochemical oxidation of O-toluidine (OT) was studied by galvanostatic electrolysis using lead dioxide (PbO2) and boron-doped diamond (BDD) as anodes. The influence of operating parameters, such as current density, initial concentration of OT and temperature was investigated. Measurements of chemical oxygen demand were used to follow the oxidation. The experimental data indicated that on PbO2 and BDD anodes, OT oxidation takes place by reaction with electrogenerated hydroxyl radicals and is favoured by low current density and high temperature. Furthermore, BDD anodes offer significant advantages over PbO2 in terms of current efficiency and oxidation rate.