Absolute Antioxidant Activity of Five Phenol-Rich Essential Oils.

Essential oils (EOs) have promising antioxidant activities which are gaining interest as natural alternatives to synthetic antioxidants in the food and cosmetic industries. However, quantitative data on chain-breaking activity and on the kinetics of peroxyl radical trapping are missing. Five phenol-rich EOs were analyzed by GC-MS and studied by oxygen-uptake kinetics in inhibited controlled autoxidations of reference substrates (cumene and squalene). Terpene-rich Thymus vulgaris (thymol 4%; carvacrol 33.9%), Origanum vulgare, (thymol 0.4%; carvacrol 66.2%) and Satureja hortensis, (thymol 1.7%; carvacrol 46.6%), had apparent kinh (30 °C, PhCl) of (1.5 ± 0.3) × 104, (1.3 ± 0.1) × 104 and (1.1 ± 0.3) × 104 M-1s-1, respectively, while phenylpropanoid-rich Eugenia caryophyllus (eugenol 80.8%) and Cinnamomum zeylanicum, (eugenol 81.4%) showed apparent kinh (30 °C, PhCl) of (5.0 ± 0.1) × 103 and (4.9 ± 0.3) × 103 M-1s-1, respectively. All EOs already granted good antioxidant protection of cumene at a concentration of 1 ppm (1 mg/L), the duration being proportional to their phenolic content, which dictated their antioxidant behavior. They also afforded excellent protection of squalene after adjusting their concentration (100 mg/L) to account for the much higher oxidizability of this substrate. All investigated EOs had kinh comparable to synthetic butylated hydroxytoluene (BHT) were are eligible to replace it in the protection of food or cosmetic products.

Calibration of Squalene, p-Cymene, and Sunflower Oil as Standard Oxidizable Substrates for Quantitative Antioxidant Testing.

The autoxidation kinetics of stripped sunflower oil (SSO), squalene (SQ), and p-cymene ( p-C) initiated by 2,2'-azobis(isobutyronitrile) at 303 K were investigated under controlled conditions by differential oximetry in order to build reference model systems that are representative of the natural variability of oxidizable materials, for quantitative antioxidant testing. Rate constants for oxidative chain propagation ( kp) and chain termination (2 kt) and the oxidizability ( kp/√2 kt) were measured using 2,6-di- tert-butyl-4-methoxyphenol, 2,2,5,7,8-pentamethyl-6-chromanol, BHT, and 4-methoxyphenol as reference antioxidants. Measured values of kp (M-1 s-1)/2 kt (M-1 s-1)/oxidizability (M-1/2 s-1/2) at 303 K in chlorobenzene were 66.9/3.45 × 106/3.6 × 10-2, 68.0/7.40 × 106/2.5 × 10-2, and 0.83/2.87 × 106/4.9 × 10-4, respectively, for SSO, SQ, and p-C. Quercetin, magnolol, caffeic acid phenethyl ester, and 2,4,6-trimethylphenol were investigated to validate calibrations. The distinctive usefulness of the three substrates in testing antioxidants is discussed.