N. V. Yanishlieva-Maslarova, Bulgarian Academy of Sciences, Sofia and I. M. Heinonen, University of Helsinki
Rosemary is one of the most effective spices, widely used in food processing. It is the only spice commercially available for use as an antioxidant in Europe and the United States. One of the main potential uses is the suppression of warmed over flavour (WOF).1 However, because of their prime use as flavouring agents, rosemary extract products are not technically listed as natural preservatives or antioxidants.
The first use of an extract of rosemary leaves as an antioxidant was reported by Rac and Ostric-Matijasevic in 1955.2 Berner and Jacobson3 obtained a patent in 1973 for production of an antioxidant extract from rosemary using oil as a solvent. Chang et al.4 reported a process for the extraction of rosemary and sage, followed by vacuum steam distillation in an edible oil or fat to obtain a colourless, odourless natural antioxidant. Bracco et al.5 described an extraction process using peanut oil, followed by micronization, heat treatment and molecular distillation. Inahata et al6 obtained a patent in 1996 for production of odourless and safe antioxidants from rosemary by repeated extraction, evaporation, purification and dissolving procedures. More recently another technique, supercritical carbon dioxide extraction, has been used to product extracts of rosemary and sage.7,8
Antioxidant properties of rosemary have been well documented.9-15 Rosemary was considered both lipid antioxidant and metal helator.12 Rosemary extract was found also to scavenge superoxide radicals.15 The application of rosemary extracts in food has resulted in a variability in the results depending on the test model being used.
Many different solvents have been used for the extraction of the antioxidative compounds.4'16-19 Chang et al.4 extracted rosemary leaves with hexane, benzene, ethyl ether, chloroform, ethylene dichloride, dioxane and methanol. The extracts (0.02%) were tested during oxidation of lard at 60°C in the dark. It was established that the greatest antioxidant activity was located in the methanol extract. The methanol extract was further purified, and the resultant fraction showed an outstanding activity in potato chips fried in sunflower oil and held at 60°C in the dark for 60 days.
Marinova et al.,17 Chen et al.,18 and Pokorny et al.19 found that the hexane extracts from rosemary were better antioxidants for lard,17,18 rapeseed and sunflower oils,19 than methanol18 or ethanol19 extracts. Hexane extract (0.05%) caused a 35-fold increase of the oxidation stability of lard determined at 100°C, and the use of 0.05% ethanol extract resulted in a 20-fold increase.17 In bulk rapeseed oil hexane extracts from rosemary and sage were also more efficient than ethylacetate or acetone extracts.20 It was established that rosemary extracts were more active than sage extracts,19,20 and that rapeseed oil was more efficiently stabilized than sunflower oil.19
The antioxidative effect of rosemary ethanol extract on butter,21, 22 as well as on filleted and minced fish during frozen storage was studied.23 Rosemary antioxidants were found suitable for deep frying in edible oils,24 especially in the presence of ascorbyl palmitate.25 Reblova et al.26 investigated the effect of acetone and ethyl acetate extracts on the changes in rapeseed oil and in an oil containing polysiloxanes during frying of potatoes. The authors established that the rosemary extract inhibited the formation of polar substances, polymers and decomposition of polyunsaturated triacylglycerols, especially in the case of rapeseed oil, and improved the sensory attributes of French fries.
Barbut et al.11 studied the effectiveness of rosemary oleoresin (RO) in turkey breakfast sausages. The authors found that RO was as effective as the combination of BHA, or butylated hydroxytoluene (BHT), with citric acid in suppressing oxidative rancidity. A standardized RO has many different phenolic components. It is thought that they act in synergy to provide antioxidant activity.
Results from the oxidation of stripped soybean oil exposed to fluorescent light, in the presence of rosmariquinone (RQ) and RO27 indicated that RO contained compounds, such as chlorophyll, pheophytin and mono- and diglycerides, which under light interfere with the antioxidant components, thus reducing the antioxidant activity. This was confirmed by the highest level of antioxidant activity exhibited by the RQ in comparison to RO.
Lai et al.28 and Murphy et al.29 investigated the antioxidant properties of RO alone or in combination with sodium tripolyphosphate (STPP) in controlling lipid oxidation in restructured chicken nuggets28 and in precooked roast beef slices29 during refrigerated and frozen storage. Stoick et al.30 studied the oxidative stability of restructured beef steaks processed with RO, tertiary butylhydroxyquinone (TBHQ), and STPP. They found that the addition of RO gave no benefit over STPP. The RO/STPP combination was equivalent to TBHQ/STPP treatment in preventing oxidation.
Wada and Fang31 observed a strong synergistic effect between rosemary extract (0.02%) and a-tocopherol (0.05%) in sardine oil at 30°C and in frozen-crushed fish meat models. The authors suggested that rosemary extract functions as a hydrogen atom donor regenerating the a-tocopheroxyl radical to a-tocopherol. Synergistic effects were also found between rosemary and sage extracts, and tocopherols or soybean meal hydrolysates in a linoleic acid emulsion.32
Basaga et al.15 reported that rosemary extract and BHT, when added as mixtures of 75:25, 50:50 and 25:75 had a synergistic effect on preventing oxidation of soybean oil. A very pronounced synergistic effect was seen between citric acid and rosemary extract.33
Concurrent with the evaluation of rosemary extracts as antioxidants to inhibit lipid oxidation in food systems, research was also focused on isolation, identification and testing of the active compounds contained in the extracts. In a study of 16 compounds isolated from rosemary Bracco et al.5 concluded that the antioxidant activity of rosemary extracts is primarily related to two phenolic diterpenes, carnosol and carnosic acid. This conclusion was confirmed by other investigators.18,34 Nakatani and Inatani35 identified rosmanol and carnosol and found that both were more effective than a-tocopherol, BHT and BHA. The same authors also isolated rosmadial from rosemary.
Several other antioxidative diterpenes such as epirosmanol and isorosmanol,36 rosmaridiphenol37 and rosmariquinone38 have been reported to contribute to the antioxidant activity of rosemary extracts. During the storage and extraction of rosemary carnosic acid is partially converted either into carnosol or into other diterpenes such as rosmanol.5,39-41
Rosmarinic acid (RA) was reported by Gerhardt and Schroter42 to be the second most frequently occurring caffeic acid ester, following chlorogenic acid, and to have antioxidant activity equivalent to that of caffeic acid. The authors detected RA in rosemary, balm, sage, thyme, oregano, marjoram, savory, peppermint, and for the first time in basil.
There are many data in the literature concerning the antioxidative properties of the individual compounds isolated from rosemary. Brieskorn and Domling43 showed that carnosic acid and carnosol were as effective as BHT and that their effectiveness was concentration dependent. The authors noted that the activity of both compounds was due to the cooperation of their ortho phenolic groups with their isopropyl group.
It was also reported that rosmanol had greater antioxidant activity than carnosol, with carnosic acid being more potent than carnosol.40,44 In soybean oil carnosic acid was found to be more active than BHT and BHA, but less active than TBHQ. Carnosic acid and carnosol showed the ability to chelate iron and were effective radical scavengers of peroxyl radicals.34 It has been established17 that the molecules of carnosol and the radicals formed from them participate in the reactions of chain initiation and propagation to a much lower degree than is the case with most natural and synthetic antioxidants.
Houlihan et al.37 found rosmaridiphenol to be more active than BHA in lard and equivalent to BHT in this test system. They reported also that RQ was superior to BHA and equivalent to BHT in controlling the oxidation of lard.38 RQ has been shown to have good antioxidant activity also in soybean oil.27 Hall et al.45 proved that RQ acted as a hydrogen-donating antioxidant. Isorosmanol and epirosmanol showed high activity in both lard and linoleic acid;36 in lard they were four times more active than BHA and BHT. Nakamura et al.46 reported that RA exhibited a significantly higher superoxide scavenging activity than ascorbic acid.
As far as the complex food systems are concerned, it is important to clarify the antioxidative behaviour not only in bulk oil, but also in oil-in-water emulsions,47-49 as well as in microsomal and liposomal systems.34 Frankel et al.41 reported that in bulk corn oil rosemary extract, carnosic and rosmarinic acids were significantly more active than carnosol. In contrast, in corn oil-in-water emulsion, the rosemary compounds were less active than in bulk oil, and the rosemary extract, carnosic acid and carnosol were more active than rosmarinic acid. The decreased antioxidant activity of the polar hydrophilic rosemary compounds in the emulsion system may be explained by their interfacial partitioning into water, thus becoming less protective than in the bulk oil system.47
Carnosol and carnosic acid were powerful inhibitors of lipid peroxidation in microsomal and liposomal systems.34
Cuvelier et al.50 found no correlation between the antioxidative effectiveness of the rosemary extracts from different pilot-plant or commercial sources and their composition in 20 specific phenols, a finding which illustrates the complex influence of the various factors on lipid oxidation stability.
23.5 Sage: antioxidant properties
Salvia officinalis L, commonly known as sage (Dalmatian sage), is used in foods for flavouring and seasoning. It was found that, along with rosemary, it had the best antioxidant activity among the numerous herbs, spices and teas tested.33,51 Its extracts are also well known as efficient antioxidants.33,50-53
Since methanol and ethanol were found to be the most suitable solvents for extraction of antioxidants from the plant materials, a number of publications have dealt with further purification of the alcohol extracts. Vacuum steam distillation4 or molecular distillation5 are recommended for use on production scale.
Since rosemary and sage belong to the Labiatae family, it is not surprising to find the same antioxidants in both plants: carnosol,50,54 carnosic acid,40,43,55-57 rosmanol,50,57 rosmadial,50 rosmarinic acid.56 Various methyl and ethyl esters of carnosol, rosmanol, and carnosic acid can be found in sage, as well as in other Labiatae plant extracts; in most cases the compounds are believed to be artefacts from the extraction procedures.39,40,43 The main antioxidative effect of sage was reported to relate to the presence of carnosic acid, carnosol and rosmarinic acid.50,56
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