ABSTRACT
The antioxidant activity of ethyl and octyl hydroxytyrosyl ethers toward lipids was determined using the Rancimat and open cup methods at high temperatures and 50 °C, respectively. The effect of the unsaturation of the matrix was evaluated using sunflower, soya, and fish refined oils. The antioxidant activities of alkyl hydroxytyrosyl ethers (HTy ethers), hydroxytyrosyl esters, and free hydroxytyrosol are similar, and are much higher than that of α-tocopherol at the same millimolar concentration. The relationship between the induction period and the concentration of the HTy ethers is a sigmoidal curve; an accurate concentration of HTy ethers is necessary to achieve maximum activity, as it increases with the level of matrix unsaturation. The presence of tocopherols in commercial oils affects the antioxidant effect of HTy ethers. Thus, the addition of a low concentration of HTy ethers results in a positive effect, whereas the effect of the addition of high amounts of ethers is slightly less than that of the phenol alone. The addition of HTy ethers to commercial refined oils increases the stability of the oils and preserves tocopherols and polyunsaturated fatty acids from oxidation, enabling the oils to maintain their nutritional properties for longer periods of time.
Subject(s)
Antioxidants/chemistry , Dietary Fats, Unsaturated/analysis , Fats, Unsaturated/chemistry , Food Preservatives/chemistry , Phenylethyl Alcohol/analogs & derivatives , Alkylation , Ethers/chemistry , Fats, Unsaturated/analysis , Fish Oils/chemistry , Food Quality , Food Storage , Hot Temperature/adverse effects , Kinetics , Lipid Peroxides/analysis , Oxidation-Reduction , Phenylethyl Alcohol/chemistry , Plant Oils/chemistry , Soybean Oil/chemistry , Sunflower Oil , Tocopherols/analysis , Tocopherols/chemistryABSTRACT
Isochroman-derivatives of the natural olive oil phenol hydroxytyrosol (HT) have been synthesised via Oxa-Pictet-Spengler reaction in high yields. Lipophilicity and antioxidant activity were determined to establish the structure-activity relationship of isochromans compared to HT, BHT and α-tocopherol. Antioxidant capacity was tested in two different media: bulk oils, using the Rancimat test, and brain homogenates, by measuring malondialdehyde (MDA) levels as a lipoperoxidation biomarker. In addition, other antioxidant assays (FRAP, ABTS and ORAC) were carried out. Rancimat and MDA results show that antioxidant activity was related with lipophilicity, directly in brain homogenates and inversely in the oils, in agreement with the polar paradox. Free o-diphenolic groups positively determined the activity in the oils, whereas reducing and radical-scavenging activities were related to the number of free hydroxyl moieties. BHT and α-tocopherol showed lower antioxidant activity than isochromans and HT. We conclude that HT-isochromans present significant potential as bioactive compounds.
Subject(s)
Antioxidants/chemistry , Antioxidants/pharmacology , Phenols/chemistry , Phenols/pharmacology , Phenylethyl Alcohol/analogs & derivatives , Animals , Antioxidants/chemical synthesis , Brain/drug effects , Brain/metabolism , Malondialdehyde/metabolism , Oxidation-Reduction , Phenylethyl Alcohol/chemistry , Phenylethyl Alcohol/pharmacology , Rats , Rats, Wistar , Structure-Activity RelationshipABSTRACT
Several works have measured free radical scavenging capacity of nut oils, since they may become a significant source of dietary fat. However, they have not considered kinetic parameters, what was the first aim of this work. Also, it was studied the possible relation between values of free radical scavenging capacity DPPH and oxidative stability (Rancimat method) in different nut (hazelnut, peanut, pistachio, walnut and almond) oils. The ranking of antioxidant capacity of nut oils, by both assays, was: pistachio>hazelnut>walnut>almond>peanut. A significant correlation was found between DPPH and Rancimat methods assays. Tocopherols appear to be the responsible compounds of this antioxidant capacity being neglictible the contribution of polyphenols. An interference effect of phospholipids, present in methanolic fraction of nut oils, was observed in the determination of polyphenols in nut oils by Folin and ortho-diphenols assays.
ABSTRACT
Antioxidant activities of lipophilic hydroxytyrosyl acetate, palmitate, oleate, and linoleate were compared with those of hydroxytyrosol, alpha-tocopherol, and butylhydroxytoluene (BHT) in both glyceridic matrix and biological systems. Aliquots of a glyceridic matrix spiked with various concentrations of antioxidant were subjected to accelerated oxidation in a Rancimat apparatus operated at 90 degrees C. The relationships between induction time (IT) and antioxidant concentration (mmol/kg) presented by hydroxytyrosol and hydroxytyrosyl acetate, palmitate, oleate, and linoleate were similar. Hydroxytyrosol and its esters showed greater antioxidant activity than alpha-tocopherol or BHT. We also evaluated the capacity of hydroxytyrosyl esters to protect proteins and lipids against oxidation caused by peroxyl radicals, using a brain homogenate as an ex vivo model. All tested compounds showed a protective effect in these systems, which was greater in preventing the generation of carbonyl groups in protein than of malondialdehyde in lipid. Inclusion of a lipophilic chain in the hydroxytyrosol molecule enhanced its antioxidant capacities in this biological model.
