Observations on the applicability of the ABTS(*+) assay to define structure-activity relationships (SARs) among phenols (AH) were based on experimental data and theoretical calculations. All AH examined (hydroxycinnamic derivatives, simple polyphenols, polyhydroxybenzoates, and flavonoids) were found to be active toward ABTS(*+). Moreover, known weak radical scavengers (i.e., coumaric and isoferulic acids) were found to be efficient or comparatively active to caffeic or rosmarinic acids in contradiction to the AH classification based on 1,1-diphenyl-2-picrylhydrazyl (DPPH) data or the bond dissociation enthalpy values. This behavior was observed both in ethanol and in buffered (pH 7.4) environment. Resorcinol and phloroglucin were found to be more active than catechol and hydroquinone, whereas, among polyhydroxybenzoates, 2,4-dihydroxybenzoic acid was the least active, in line with the DPPH and theoretical data. Therefore, it can be argued that the ABTS(*+) assay may give an indication for the presence of antioxidants in a certain system but SARs cannot be readily inferred.

Oregano vulgare L. ssp. hirtum (Greek oregano), Salvia fruticosa (Greek sage), and Satureja hortensis (summer savory) were examined as potential sources of phenolic antioxidant compounds. The antioxidant capacities (antiradical activity by DPPH* test, phosphatidylcholine liposome oxidation, Rancimat test) and total phenol content were determined in the ethanol and acetone extracts of the dried material obtained from the botanically characterized plants. The ground material was also tested by the Rancimat test for its effect on the stability of sunflower oil. The data indicated that ground material and both ethanol and acetone extracts had antioxidant activity. Chromatographic (TLC, RP-HPLC) and NMR procedures were employed to cross-validate the presence of antioxidants in ethanol and acetone extracts. The major component of all ethanol extracts was rosmarinic acid as determined by RP-HPLC and NMR. Chromatography indicated the presence of other phenolic antioxidants, mainly found in the acetone extracts. The presence of the flavones luteolin and apigenin and the flavonol quercetin was confirmed in the majority of the extracts by the use of a novel (1)H NMR procedure, which is based on the strongly deshielded OH protons in the region of 12-13 ppm without previous chromatographic separation. This deshielding may be attributed to the strong intramolecular six-membered ring hydrogen bond of the OH(5)...CO(4) moiety.

Virgin olive oil samples with similar oxidative stabilities and fatty acid compositions were stored for 24 months. Changes in the lipid substrate were followed by peroxide value and K(232) measurements. HPLC was used to evaluate changes in the alpha-tocopherol, pigment, and squalene contents. Total polar phenol content was measured colorimetrically. The loss of alpha-tocopherol and carotenoids was comparable with that of polar phenol content, suggesting an active participation in autoxidation. The limited role of squalene in autoxidation was further confirmed using an olive oil model and in the presence of alpha-tocopherol. Pheophytin a degradation was high, although spectrometric estimation of chlorophyll content did not indicate so. Evaluation of pheophytin a activity at three different levels of addition on the oil model indicated a concentration-dependent antioxidant role more pronounced at elevated temperatures, which could be partially due to the activity of certain degradation products.

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Differences in the antioxidant activity of some biosynthetically related ferulic acid derivatives induced by the presence of characteristic groups (-COOH, -CHO, -CH(2)OH, -CH(3), and -COOC(2)H(5)) at the end of their carbon side chain were investigated using both experimental and computational methods. The relative order of the scavenging activity toward the DPPH radical derived from kinetic studies was isoeugenol approximately coniferyl alcohol >> ferulic acid approximately coniferyl aldehyde approximately ethyl ferulate. In bulk oil autoxidation (45 degrees C) the same order of activity was obtained. In the o/w emulsion autoxidation, lipophilicity of the phenols was the determining factor because the least polar compounds bearing -CH(3) and -COOC(2)H(5) were the most effective ones. The order of activity based on the O-H bond dissociation enthalpy (BDE) and ionization potential (IP) values, calculated by the density functional theory (DFT) method, was in accordance with the experimental radical scavenging order and with the electron-donating/withdrawing properties of the characteristic groups. Other molecular descriptors could not complement the experimental findings.

Virgin olive oil samples with similar oxidative stabilities and fatty acid compositions were exposed to 12100 lx (25 +/- 1 degrees C) in closed bottles until bleached. The observed low changes in the substrate and polar phenols were related to oxygen availability. HPLC monitoring showed that pheophytin agradual degradation (> 90%) was accompanied by a considerable alpha-tocopherol loss (22-35%) due to the reaction of the latter with singlet oxygen. No changes were recorded for carotenoids, which acted as physical quenchers and light filters. Squalene loss was confined (4-12%). Complementary experiments on the activity of pheophytin a, using olive oil models, indicated a concentration dependence, enhanced by oxygen availability. In closed bottles, the degradation rate constant was higher at low amounts of pheophytin a. Squalene was preferentially consumed to protect alpha-tocopherol. An urgent change in the practice of packaging is needed to preserve the precious characteristics of the product during commercialization.

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