Essential oils of Origanum vulgare L. subsp glandulosum (Desf.) letswaart from Tunisia: chemical composition and antioxidant activity

BACKGROUND: Characterisation of the essential oils from O. glandulosum collected in three locations of Tunisia, chemical composition and the evaluation of their antioxidant activities were carried out. RESULTS: The essential oils from Origanum vulgare L. subsp. glandulosum (Desf.) letswaart collected from three localities of north Tunisia - Krib, Bargou and Nefza - were obtained in yields of 2.5, 3.0 and 4.6% (v/w), respectively. The essential oils were analysed by GC and GC/MS and assayed for their total phenolics content, by the Folin-Ciocalteu method, and antioxidant effectiveness, using the 2,2-diphenyl-1-picrylhydrazil (DPPH) radical scavenging assay. The main components of these essential oils, from Nefza, Bargou and Krib, were p-cymene (36%, 40% and 46%), thymol (32%, 39% and 18%), gamma-terpinene (24%, 12% and 16%) and carvacrol (2%, 2% and 15%), respectively). The ability to scavenge the DPPH radicals, expressed by IC50, ranged from 59 to 80 mg L-1. The total phenolic content, expressed in gallic acid equivalent (GAE) g kg(-1) dry weight, varied from 9.37 to 17.70 g kg(-1) dw. CONCLUSIONS: A correlation was identified between the total phenolic content of the essential oils and DPPH radical scavenger capacity. The occurrence of a p-cymene chemotype of O. glandulosum in the northern region of Tunisia is demonstrated.

Antioxidant activity and cytotoxicity of solubilized C60 and its conjugates with butylated hydroxytoluene

It has been described that fullerenes (C60) present interesting properties with potential application in clinical conditions related to oxidative stress. One of the most prominent features of fullerenes is the ability to quench free radicals. However, because of its poor solubility, this has been studied mostly in organic solutions, while the antioxidant activity and cytotoxicity of fullerenes and their derivates in aqueous medium is not well characterized. The antioxidant capacity of synthesised C60-conjugates has been investigated and its was higher comparing to C60 isolated. The aim of this study was to assess the viability of C60-conjugates by determining its antioxidant activity and cytotoxicity in bio-relevant media.

Regulation of antioxidant enzymes gene expression in the yeast Saccharomyces cerevisiae during stationary phase

Gene expression of three antioxidant enzymes, Mn superoxide dismutase (MnSOD), Cu,Zn superoxide dismutase (Cu,ZnSOD), and glutathione reductase (GR) was investigated in stationary phase Saccharomyces cerevisiae during menadione-induced oxidative stress. Both GR and Cu,ZnSOD mRNA steady state levels increased, reaching a plateau at about 90 min exposure to menadione. GR mRNA induction was higher than that of Cu,ZnSOD (about 14-fold and 9-fold after 90 min, respectively). A different pattern of response was obtained for MnSOD mRNA, with a peak at about 15 min (about 8-fold higher) followed by a decrease to a plateau approximately 4-fold higher than the control value. However, these increased mRNA levels did not result in increased protein levels and activities of these enzymes. Furthermore, exposure to menadione decreased MnSOD activity to half its value, indicating that the enzyme is partially inactivated due to oxidative damage. Cu,ZnSOD protein levels were increased 2-fold, but MnSOD protein levels were unchanged after exposure to menadione in the presence of the proteolysis inhibitor phenylmethylsulfonyl fluoride. These results indicate that the rates of Cu,ZnSOD synthesis and proteolysis are increased, while the rates of MnSOD synthesis and proteolysis are unchanged by exposure to menadione. Also, the translational efficiency for both enzymes is probably decreased, since increases in protein levels when proteolysis is inhibited do not reflect the increases in mRNA levels. Our results indicate that oxidative stress modifies MnSOD, Cu,ZnSOD, and GR gene expression in a complex way, not only at the transcription level but also at the post-transcriptional, translational, and post-translational levels.

Chemical composition and antioxidante activity of Tunisian Origanum glandulosum Desf. essential oil and volatile oil obtain by supercritical CO2 extraction

Dried flowers and leaves of Origanum glandulosum Desf. were submitted to hydrodistillation (HD) and supercritical fluid extraction with CO2 (SFE). The essential oils isolated by HD and volatile oils obtained by SFE were analysed by GC and GC/MS. Total phenolics content and antioxidant effectiveness were performed. The main components of the essential oils from Bargou and Nefza were: p-cymene (40.4% and 39%), thymol (38.7% and 34.4%) and γ- terpinene (12.3% and 19.2%), respectively. The major components obtain by SFE in the volatile oil, from Bargou and Nefza, were: p-cymene (32.3% and 36.2%), thymol (41% and 40%) and γ-terpinene (20.3% and 13.3%). Total phenolic content, expressed in gallic acid equivalent (GAE) g kg-1 dry weight, varied from 12 to 27 g kg-1 dw, and the ability to scavenge the DPPH radicals, expressed by IC50 ranged from 44 to143 mg L-1.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.