ISSN: 1579-4377

APPLICATION OF PHENOLIC ANTIOXIDANTS IN FOOD PRODUCTS

Jan Pokorny, Institute of Chemical Technology, Department of Food Chemistry and Analysis, CZ-16628 Prague, Czech Republic; jan.pokorny@vscht.cz

ABSTRACT Plant phenolics are the most important group of natural antioxidants. They are present in almost all plants so that their daily consumption in human diet is about 1 g. They consist mostly of phenolic acids, flavonoids, anthocyanins and their glycosides. Less polar substances, such as tocopherols, lignans or resins, may be added to fats and oils increasing their stability on storage and heating. More polar phenolics are advantageous for stabilization of food dispersions. Rosemary and sage resins were found efficient in frying fats. Particularly high content of phenolics is found in spices, tea leaves, roasted coffee and cocoa beans, and in red wine. Attempts to increase the antioxidant levels in blood stream were not very efficient as most phenolics are inactivated before or immediately after the resorption through the intestine wall. The need of antioxidants in vivo would be lower if the intake of polyunsaturated fatty acid esters would be kept sufficient, but not excessive. KEYWORDS Application, phenolic, antioxidans, food, products.

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INTRODUCTION Why to consume phenolic antioxidants Phenolic antioxidants react with free lipidoxy or lipidperoxy free radicals, produced in course of lipid oxidation [1], preventing thus their further autoxidation [2]. The inhibition of lipid autoxidation is important not only in foods during their storage or heating, but also to reduce the oxidation of lipids after ingestion and absorption through the intestinal wall. Where phenolic substances are located in plants Phenolic substances are mainly deposited [3] in leaves or bark (in case of trees or bushes), together with other waste products. Phenolic substances also serve as a protection against herbivores or other pests, including human consumers, as the astringent taste repeals them against consumption. In lesser amounts, phenolic compounds are present in seeds and other parts of the plant. Phenolic antioxidants in seeds Most seeds contain large amounts of polyunsaturated oils and phenolic antioxidants necessary to protect polyunsaturated fatty acids in oil against autoxidation until the next crop. During oilseed processing, less polar antioxidants are co-extracted with oil, while more polar antioxidants, insoluble in the extraction solvent, remain in the extracted meal. The most common natural antioxidants in oils are tocopherols (and tocotrienols in some cases). Tocopherols possess both a vitamin activity and the activity as antioxidants. As a vitamin, a-tocopherol is the most powerful antioxidant in vivo, but as an inhibitor of oxidation, d-tocopherol is the most efficient representative, followed by ?- and tocopherols, while a-tocopherol is the least active compound [4]. The relative antioxidant activity of tocotrienols is about the same as that of tocopherols. Some tocopherol oxidation products possess antixidant activity as well [5]. Another group of phenolic antioxidants in oils belongs to lignans (secoiridoids) and their decomposition products [3]. A typical representative is sesamol, an active antioxidant in sesame oil. Another rich source is linseed oil, too. Even some non-phenolic substances possess antioxidant activities, such as some phytosterols or squalene. Carotenes and carotenoids may contribute to the oxidative stability of oils, if they were not removed by refining. Among more polar antioxidants in the extracted meal, various phenolic acids, such as ferulic or sinapic acids, and their esters, or chlorogenic acid are of importance. Rapeseed extracted meals are extraordinary rich source of sinapic acid, bound to choline as an ester [7], but it is not active as an antioxidant. Extracted meals of evening primrose seeds contain several efficient phenolic antioxidants so that their extracts are active both in oils and their emulsions [9]. Plant antioxidants present in leaves All plant leaves contain phenolic substances, sometimes in high amounts. e. g. in tea leaves. Most phenolic antioxidants are flavonoids, such as catechins, of different structures and antioxidant activities [10]. As they are rather polar and their glycosides are very polar, some derivatives are only sparingly soluble in oil, accumulating in the water phase. However, in food emulsions, they are active at least on the interface.

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Natural antioxidants from herbs and spices were recently reviewed [11]. Many among them are well known because of their phenolics content, On contrary, less familiar materials, such as sweetgrass (Hierochloe odorata Walhl.), used for flavouring certain types of vodka, was also found very effective as an antioxidant [12]. Some plant leaves are applied to food, and are widely used. Perhaps the best known antioxidants from plant leaves are leaves from green and black (fermented) tea. Content of catechins is particularly high in green tea, but its infusions are less concentrated. During the tea fermentation, about 50 % phenolic substances are converted into black tea pigments theaflavins and thearubigins nevertheless, they have some residual activity, too, and black tes, prepared at higher concentrations, is a very good source of antioxidants in Europe [13]. A few cups of strong tea would supply nearly the daily portion of antioxidants. Extracts from tea wastes are commerically available. Herbal teas also contain phenolic substances, but in smaller amounts. Spices contribute to the daily consumption of antioxidants, but their content in the diet is low. The highest antioxidant activities were observed in leaves of Labiatae plants, such as rosemary, sage, savory, and oregano. Their advantage is that they may be first used for the isolation of essential oil, which is distilled, and active resins are left in nonvolatile residues. They are commercially available at reasonable prices. Therefore, they are particularly suitable for food stabilization [14]. resins from sage and rosemary were found active in refined sunflower [15] and rapeseed [16] [17] oils. We have found [18] them efficient for deep fat frying [18] and for stabilization of bergamot oil, especially when added with dihydropyridine derivatives [19]. Fruits as a source of plant phenolics Fruits are also good source of antioxidants, but not so rich as leaves. The best known fruits are olives, which contain a variety of antioxidants [20]. Unfortunately, olives are too expensive to apply them as a regular source of antioxidants. Nevertheless, they might be added to food both as a flavouring and as a factor inhibiting the oxidation. Sources of antioxidants from fruits would be less expensive, but waste products from the food processing would be also acceptable. A typical example are peanut skin extracts [21], which contain several phenolic antioxidants. Another example is acerola (Bermuda cherries, Malpighia glabra) fruits [22]. Their content of phenolic antioxidants (mainly flavonoids) is low, but they contain very high amount of ascorbic acid, acting as a synergist, which has a pronounced positive effect on the plant stability. Two other fruits should be mentioned here, namely coffee beans and cocoa beans. Both are consumed as a beverage in such an extent [14] that they contribute substantially to the total antioxidants consumed [14]. Cocoa powder is used for the production of chocolate, an important source of antioxidants for children. A group of fruits contains anthocyanin pigments, sometimes in large amounts, which contribute as an important component to the total ingestion of antioxidants (up to 60 %) [14], especially some vaeities of red wine. Changes of antioxidants during oxidation Antioxidants are changed by reactions with free lipid radicals. The first reaction product is a free radical of the respective antioxidant, which is substantially more stable than a lipidoxy or lipidperoxy radical. It may react in three ways: 1. reaction with another antioxidant free radical with formation of a dimer; dimers usually possess an antioxidant activity, too; 2.

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reaction with a lipidoxy or lipidperoxy radical with formation of a co-polymer; 3. reaction with an active lipid free radical with formation of a biradical, which is rapidly isomerized into a quinone; quinones may react with amine and thiol groups with formation of copolymers, often possessing moderate antioxidant activities [22] [23]. The reaction is partially reversible if suitable synergists are present. These susbstances are usually not included in the calculation of total antioxidants present, which is particularly important in cases, when the maximum permitted content is limited. Safety of these reaction products is mostly unknown; we only hope it is better than that of the original phenolics.. Application of plant phenolics as antioxidants in vivo The daily consumption of phenolic natural antioxidants is about 1 g, which is quite sufficient for regulating the level of free radicals in blood, if the polyunsaturated fatty acid consumption is low, but still sufficient from the nutritional standpoint. Further increase of antioxidant consumption is dubious. The human body considers phenolics as toxic substances so that most ingested antioxidants are transformed into undigestible derivatives in the small intestine befor their absorption, and partially also after the absorption. Therefore, only about 10 % are really absorbed, and can inactivate free radicals. To increase the daily ingestion of phenolics to more than 2 g could already bring some health risks. The better way to eliminate excess free radicals is to consume lower amounts of polyunaturated fatty acids in the diet [14]. CONCLUSIONS The traditional human diet is relatively rich in phenolics. They are moderately toxic, but on the same level as synthetic antioxidants. A diet consisting of sufficient amount of fruit and vegetables, whole grain cereals, and tea, coffee or red wine as bevearges brings enough phenolic antioxidants to the body so that no massive addition of other antioxidants is necessary. It is important to limit the consumption of total lipid polyunsaturated fatty acids, in order to reduce the level of free radicals in the body. REFERENCES
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