776 Nedyalka V.

Yanishlievaa Emma Marinovaa Jan Pokornyb Institute of Organic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria b Faculty of Food and Biochemical Technology, Prague Institute of Chemical Technology, Prague, Czech Republic
a

DOI 10.1002/ejlt.200600127

Eur. J. Lipid Sci. Technol. 108 (2006) 776793

Natural antioxidants from herbs and spices

There is a growing interest in natural antioxidants found in plants because of the worldwide trend toward the use of natural additives in food and cosmetics. Herbs and spices are one of the most important targets to search for natural antioxidants from the point of view of safety. This review presents the results on stabilization of lipids and lipidcontaining foods with different herbs and spices (ground materials or extracts) and reports the structure of the main antioxidatively acting compounds isolated from them. The review presents information about the antioxidative effects of rosemary, sage, oregano, thyme, ginger, summer savory, black pepper, red pepper, clove, marjoram, basil, peppermint, spearmint, common balm, fennel, parsley, cinnamon, cumin, nutmeg, garlic, coriander, etc. Among the herbs of the Labiatae family, rosemary has been more extensively studied and its extracts are the first marketed natural antioxidants. Sage and oregano, which belong to the same family, have gained the interest of many research groups as potential antioxidants. Keywords: Herbs, spices, natural antioxidants, antioxidant activity.

1 Introduction
Lipid oxidation occurring in food products is one of the major concerns in food technology. It is responsible for rancid odors and flavors of the products, with a consequent decrease in nutritional quality and safety caused by the formation of secondary, potentially toxic compounds. The problem of ensuring a high quality of lipids and lipid-containing products and prolonging their storage time is directly associated with their optimum stabilization by addition of suitable antioxidants. This is very important to human health protection and also economically important. There is a growing interest in natural antioxidants found in plants because of the world-wide trend toward the use of natural additives in food and cosmetics. Herbs and spices are one of the most important targets to search for natural antioxidants from the point of view of safety [16]. Since the early work of Chipault et al. [79] who have examined more than 70 spices and herbs, the interest in the antioxidative activity of spices has increased and led to an increase in information about the compounds and mechanism involved [1013].

2 Ground herbs and spices

In the evaluation of spices, some investigations have been carried out using the whole spice [1418]. Tab. 1 illustrates the importance of the substrate used for evaluating the antioxidative activity of the additives. Rosemary and sage were the most effective antioxidants in lard [7, 19] and both spices were found to have a low redox potential in sausages indicating antioxidative activity [2022]. However, in an oil-in-water emulsion, clove was the most effective spice [8, 23, 24]. In general, the stabilization factors obtained for the spices in emulsions were several times greater than those in lard, indicating a higher efficiency against oxidation in the emulsion [25]. Shahidi et al. [26] reported that the antioxidative activity of ground clove, ginger, oregano, sage and thyme in meat lipids was concentration dependent, but clove was the most effective, followed by sage and then rosemary. Ginger and thyme exerted the weakest effect. Dried leaves of rosemary added to cooked pork meat balls retarded the development of warmed over flavor (WOF) during cold storage [27]. Tsimidou et al. [28] found that 1% oregano was equivalent to 200 ppm butylated hydroxyanisol (BHA) in controlling oxidation of mackerel oil. For an oil-in-water emulsion, addition of 0.15% of dried leaves of summer savory, or more significantly of rosemary, resulted in a significantly better antioxidative protection than the addition of 80 ppm propyl gallate (PG) [29]. The industrial treatment with microwaves of black pepper, basil and sage did not modify the antioxidant properties of these herbs and spices [30]. www.ejlst.com

Review Article

Correspondence: Nedyalka V. Yanishlieva, Institute of Organic Chemistry, Bulgarian Academy of Sciences, kv. Geo Milev, Acad. G. Bonchev Str., Blok 9, 1113 Sofia, Bulgaria. Phone: 1359 2 9606178, Fax: 1359 2 8700225, e-mail: nelly@orgchm. bas.bg

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Tab. 1. Relative antioxidative effectiveness (RAE) of spices and herbs, evaluated as whole plant material in different substrates. Spice, herb, tea Marjoram, nutmeg, white pepper, rosemary, sage, coriander, black pepper 32 different 19 different 32 different 10 different Allspice, red paprika, savory, marjoram, black pepper, white pepper, coriander 15 different 12 different Substrate Lard Lard Oil-in-water-emulsion Oil-in-water-emulsion Oil-in-water-emulsion Sausage, water Sausage, water Ground chicken meat RAE Rosemary . sage . nutmeg . white pepper . marjoram Rosemary . sage . oregano . nutmeg . thyme Clove . cinnamon . sage . mace . oregano Clove . turmeric . allspice . mace . rosemary Clove . allspice . cinnamon . nutmeg . ginger Allspice . red paprika . savory . marjoram . black pepper Sage . rosemary . paprika . marjoram . aniseed Marjoram . caraway . peppermint . clove References [19] [7] [23] [8] [24] [20] [21] [22]

The influence of the type of food system on the stabilization factor of different spices is presented in Tab. 2 [31]. Tab. 2. Stabilization factor, F, of different herbs and spices in four foods [31]. Substrate Lard Oil-in-water Minced Mayonemulsion pork meat naise 63 0.1 16.7 10.2 7.8 7.9 7.9 6.8 8.8 15.9 9.2 25 0.25 ,5.3 ,5.3 ,5.3 ,7.2 1.0 6.0 1.3 4.5 5.3 20 0.2 1.4 2.2 2.4 8.5 1.5 1.8 1.0 0.9 0.9

The first use of an extract of rosemary leaves as an antioxidant was reported by Rac and Ostric-Matijasevic [32]. Antioxidant properties of rosemary have been well documented [3342]. Rosemary was considered as both lipid antioxidant and metal chelator [33]. Rosemary extracts were found also to scavenge superoxide radicals [35]. Many different solvents have been used for the extraction of the antioxidative compounds [4347]. Chang et al. [43] 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 7C in the dark. It was established that the greatest antioxidant activity was located in the methanol extract. Marinova et al. [45], Chen et al. [46] and Pokorny et al. [47] found that the hexane extracts from rosemary were better antioxidants for lard [45, 46], rapeseed and sunflower oils [47] than the methanol [46] or ethanol [45, 47] extracts. In rapeseed oil, hexane extracts from rosemary and sage were also more efficient than ethyl acetate or acetone extracts [48]. The antioxidative effect of rosemary ethanol extract on butter has also been studied [49]. Rosemary antioxidants were found suitable for deep-frying of edible oils [50], especially in the presence of ascorbyl palmitate [51]. Reblova et al. [52] investigated the effect of acetone and ethyl acetate extracts on the changes in rapeseed oil and in an oil containing polywww.ejlst.com

Storage temperature [7C] 99 Spice, concentration 0.2 in fat [%] Clove 1.8 Rosemary 17.6 Sage 14.2 Oregano 3.8 Summer savory 1.6 Thyme 3.0 Ginger 1.8 Curcuma 2.9 Nutmeg 3.1

F = IPwith additive/IPwithout additive (IP, induction period).

3 Rosemary (Rosmarinus officinalis L.)

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.

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 Several other antioxidative diterpenes such as epirosmanol 5 and isorosmanol 6 [58], rosmaridiphenol 7 [59] and rosmariquinone (RQ) 8 [60] have been reported to contribute to the antioxidant activity of rosemary extracts (Fig. 1). During the storage and extraction of rosemary, carnosic acid is partially converted either into carnosol or into other diterpenes such as rosmanol [55, 61, 62]. Rosmarinic acid (RA) 9 (Fig. 1) was reported by Gerhardt and Schrter [63] 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, peppermint, and for the first time in basil. Recently, Bano et al. [64] studied the distribution of phenolic diterpenes, flavones and RA during the development of leaves, flowers, stems and roots of rosemary. There are many data in the literature concerning the antioxidative properties of the individual compounds isolated from rosemary. Briskorn and Domling [65] 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.

siloxanes during frying of potatoes. The authors established that the rosemary extracts inhibited the formation of polar substances and polymers and the decomposition of polyunsaturated triacylglycerols. Trojakova et al. [53] reported that rosemary efficiently protects tocopherols naturally present in rapeseed oil. Wada and Fang [54] observed a strong synergistic effect between rosemary extract (0.02%) and a-tocopherol (0.05%) in sardine oil at 30 7C and in frozen-crushed meat models. The authors suggested that rosemary extract functions as a hydrogen atom donor regenerating the atocopheryl radical to a-tocopherol. A very pronounced synergistic effect was seen between citric acid and rosemary extract [7]. Concurrent with the evaluation of rosemary extracts as antioxidants to inhibit lipid oxidation, 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. [55] concluded that the antioxidant activity of rosemary extracts is primarily related to carnosol 1 and carnosic acid 2 (Fig. 1). Nakatani and Inatani [56] identified rosmanol 3 (Fig. 1) and carnosol and found that both were more effective than a-tocopherol, BHT and BHA. The same authors [57] isolated also rosmadial 4 from rosemary (Fig. 1).

Fig. 1. Formulae of the antioxidatively acting compounds I.

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 It was also reported that rosmanol had greater antioxidant activity than carnosol [56], with carnosic acid being more potent than carnosol [61, 66]. 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 [67]. Houlihan et al. [59] 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 [60]. RQ has been shown to have good antioxidant activity also in soybean oil [68]. Hall et al. [69] proved that RQ acted as a hydrogen-donating antioxidant. Isorosmanol and epirosmanol showed high activity in both lard and linoleic acid [58]; in lard, they were four times more active than BHA and BHT. Nakamura et al. [70] 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 behavior not only in bulk oil, but also in oil-in-water emulsions [7173], as well as in microsomal and liposomal systems [67]. Frankel et al. [71] reported that in bulk corn oil, rosemary extract, carnosic acid and RA 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 in the rosemary extract, carnosic acid and carnosol were more active than RA. 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 [71]. Carnosol and carnosic acid were powerful inhibitors of lipid peroxidation in microsomal and liposomal systems [67].

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plants [80]: carnosol [76], carnosic acid [61, 65, 81, 82], rosmanol [76, 82], rosmadial [76], and RA [80, 81]. 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 artifacts from the extraction procedures [63, 65]. The main antioxidative effect of sage was reported to relate to the presence of carnosic acid, carnosol, and RA [76, 81]. The list of the antioxidants isolated from sage is growing [83], e.g. 9-ethylrosmanol ether 10 [74], luteolin-7-O-bglucopyranoside 11 [84], 6-O-caffeoyl-b-D-fructofuranosyl-(2?1)-a- D -glucopyranoside 12 and 1-O-caffeoylb-D-apiofuranosyl-(1?6)-b-glucopyranoside 13 [85] (Fig. 2). Lu and Foo [83] studied the antioxidant activity of flavonoids and phenolic acids isolated from sage, using three different test methods, namely DPPH free radical, superoxide anion radical, generated from the xanthine/xanthine oxidase system, and reduction of the phosphomolybdenum complex. The authors found that the antioxidant activity of the flavonoids was variable and that those with a catechol B-ring (luteolin glycosides) were more active than those without (apigenin glycosides).

5 Oregano (Oreganum vulgare L.)

Oregano is very often used as a spice and its flavor is highly favorable to consumers all over the world. It is valued also for its antimicrobial and antioxidant properties. Dry oregano, as well as extracts obtained by using solvents of different polarity (hexane, dichloromethane, methanol) have been tested as retarders of lipid oxidation in model systems or in real food products [7, 9, 28, 86]. Abdalla and Roozen [77] reported that oregano acetone extract was more active in sunflower oil than in its 20% oil-in-water emulsion during oxidation in the dark at 60 7C. Other subspecies of oregano, e.g. Origanum onites, Satureja thymba, Coridothymus capitatus, and Origanum dictamnus were also investigated [8789]. The water-soluble fraction of the methanol extract of oregano leaves was purified with polyamide chromatography to give five polar compounds [90, 91] RA, caffeic acid 14, protocatechuic acid 15, a new glucoside of protocatechuic acid 16, and a derivative of RA, 2-caffeoyloxy3-[2-(4-hydroxybenzyl)-4,5-dihydroxy] phenylpropionic acid 17 (Fig. 3). In the ethyl ether layer from the ethanol extract, Vekiari et al. [86, 92] identified four flavonoids www.ejlst.com

4 Sage (Salvia officinalis L.)

Salvia officinalis L., commonly known as sage, is used in foods for flavoring and seasoning. It was found that, along with rosemary, it has the best antioxidant activity among the numerous herbs and spices tested [7, 8]. Its extracts are also well known as efficient antioxidants [7479]. Since methanol and ethanol were found to be the most suitable solvents for extraction of antioxidants from plant materials, a number of publications have dealt with further purification of the alcohol extracts. Vacuum steam distillation [43] or molecular distillation [55] 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

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Fig. 2. Formulae of the antioxidatively acting compounds II.

Fig. 3. Formulae of the antioxidatively acting compounds III.

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 apigenin 18, eriodictyol 19, dihydroquercetin 20, and dihydrokaempherol 21. In the hexane extract a-, b-, gand d-tocopherols were found [88] (Fig. 3). The essential oil obtained from oregano contained carvacrol 22 and thymol 23 [87, 93] (Fig. 3). According to Lagouri et al. [87], the antioxidative effect of oregano may be related to the presence of these isomers. Yanishlieva et al. [94] established that thymol and carvacrol differed in the mechanism of their inhibiting action at room temperature, which depended on the character of the lipid medium. Thymol was a better antioxidant in triacylglycerols of sunflower oil than in triacylglycerols of lard.

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strong antioxidant [97]. The antioxidative effect of thyme ethanol extract is associated with the high content of carvacrol and thymol [98]. Antioxidative activity was found in the weakly acidic fraction, which was repeatedly purified by chromatography to give five new diphenyldimers of thymol and carvacrol 25 29 [99] (Fig. 4) and highly methoxylated flavonoids 3032 [100] (Fig. 4).

7 Ginger (Zingiber officinale) and turmeric (Curcuma domestica L.)

The rhizome of the popular ginger species, Zinger officinale, is currently widely used as a spice and food seasoning due to its sweet aroma and pungent taste. It has been known to have antioxidant activity [101, 102]. It has been found that the extracts of fresh ginger showed a higher activity than that of stored ginger [103]. The non-volatile fraction of the dichloromethane extract of dried ginger was purified by CC and HPLC to yield more than 30 compounds, 16 of which were new [104]. These compounds were structurally classified into gingerol-related compounds and diarylheptanoids (compounds 3346, Fig. 5), and their structure-antioxidant

6 Thyme (Thymus vulgaris L.)

Thyme comes originally from the regions around the Mediterranean and is used as cough medicine. It has also been commonly used as one of the culinary herb spices for adding flavor and deodorizing. The phenolic monoterpenes in thyme, thymol and carvacrol, are the primary compounds that contribute to the characteristic aroma of its essential oil [95]. They are also known to inhibit lipid peroxidation [94, 9698]. pCumene-2,3-diol 24 (Fig. 4) isolated from thyme is also a

Fig. 4. Formulae of the antioxidatively acting compounds IV.

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Fig. 5. Formulae of the antioxidatively acting compounds V.

relationship in an aqueous ethanolic solution of linoleic acid was examined [104, 105]. The pungent components, gingerol 33, shogaol 34 and zingerone 35, were reported to show high activity [106]. The dried rhizome of turmeric is widely used as a spice, as a coloring agent and as a folk medicine. The yellow pigment curcumin 46 and the curcumin derivatives 4756 (Fig. 6) are known to possess potent antioxidant activity [104106]. Curcumin suppressed the oxidation of methyl linoleate in organic homogeneous solution and aqueous emulsions, soybean phosphatidylcholine liposomal membranes and rat liver homogenate induced by free

radicals [107]. A mechanism for the dimer production has been proposed and its relation to curcumins antioxidant activity has been discussed [108]. The results indicated that the dimer is a radical-terminating product formed during the initial stage of the process [108]. Matsuda and Jitoe [109] reported that the antioxidant activity of cassmunins AC was stronger than that of curcumin, and their antiflammatory activity was also stronger than that of curcumin. Jitoe et al. [101] studied the relationship between the antioxidant activity of nine tropical ginger extracts and www.ejlst.com

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Fig. 6. Formulae of the antioxidatively acting compounds VI.

their curcuminoid quantities in a linoleic acid-ethanol system. The data indicated that the antioxidant activities of the ginger extracts were greater than that estimated from the quantity of curcuminoid found in the extracts. Obviously, there is a synergism between the compounds present in the extracts.

Yanishlieva and Marinova [110] established that the ethanol extract of the spice exhibited a good antioxidative effect in triacylglycerols of sunflower oil at 100 7C, as well as in commercial sunflower oil [111]. The effect of the extract in lard is stronger at room temperature than at 100 7C [112]. Addition of 0.10.5% of the ethanol extract of summer savory to sunflower oil decreased the oxidative and thermal changes in it during simulated deep-fat frying [113]. The effect of ca. 200 ppm of freeze-dried methanol extract of summer savory, added to an oil-in-water emulwww.ejlst.com

8 Summer savory (Satureja hortensis L.)

Summer savory is an annual culinary herb widely used in the food industry.

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sion dressing, was comparable to the effect of PG [29]. The antioxidative effect found for dark storage changed to a pro-oxidative effect during light exposure (850 lx). The chlorophyll present in summer savory is believed to have acted as an efficient sensitizer causing an acceleration of the oxidation process [29]. Dorman and Hiltunen [114] characterized the antioxidant properties of an acidified aqueous methanol extract from commercially available summer savory. The authors found that the ethyl acetate-soluble subfraction of the crude methanol extract was the most effective as antioxidant. Antioxidative compounds isolated from summer savory are RA [115], carnosol and carnosic acid [116], carvacrol and thymol in the essential oil [93, 117]. Portuguese savory oil does not contain thymol [118].

9 Other herbs and spices

Supercritical carbon dioxide extracts of ground black pepper (Piper nigrum L.) have been found superior in reducing lipid oxidation of cooked ground pork [119]. The antioxidative activity of black pepper can, at least partially, be ascribed to the presence of glycosides of the flavonoids kaempherol, rhamnetin and quercetin [120], as well as to the phenolic amides 5761 [121] (Fig. 7). Chili pepper (Capsicum frutescence L.) and red pepper (C. annum L.) contain capsaicin 62 (Fig. 7), a pungent principle showing significant antioxidative properties. A new antioxidant, capsaicinol 63 (Fig. 7), was isolated from chili pepper [95]. Marcus et al. [122] reported the change in antioxidant content in red pepper (paprika) as a function of ripening and some technological factors.

Fig. 7. Formulae of the antioxidatively acting compounds VII.

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 Gallic acid 64 and eugenol 65 (Fig. 7) have been identified as the major active components in clove (Eugenia caryophyllata) [123]. It has been established that isoeugenol 66 (Fig. 7), more rarely found in nature, exhibited higher antioxidative efficiency than eugenol during methyl oleate oxidation [124] and lard and sunflower oil oxidation [125]. Eugenol and isoeugenol have also an inhibiting effect on the peroxidation of lecithin induced by the Fe21-H2O2 system [126]. Extracts of licorice (Glycyrrhiza glabra L.) also possess antioxidant activity [127, 128]. The antioxidant effect of licorice phenolics is well known [129]. Gordon and An [128] isolated eight purified flavonoids from the solvent extracts of licorice and studied their antioxidant effectiveness in lard at 100 7C. The authors supposed a synergistic effect of the flavonoid mixture that may be responsible for the high activity observed. Different flavonoids were also isolated from the extract of the sage Salvia nemorosa L. [130], an aromatic perennial herb of the southern European region, and from Anthriscus sylvestris [131], a Serbian plant species used in folk medicine and in salad dressing. The flavonoids, and especially flavonoid glycosides, can be found in nearly all herbs and spices tested [132].

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The antioxidant extracts prepared from the seeds of the African spice Aframomum danielli were more effective than BHTand a-tocopherol in stabilizing refined peanut oil [133]. Numerous other herbs and spices, or spice vegetables, have been shown to possess antioxidative properties, e.g. marjoram [14, 25, 134140], basil [63, 110, 111, 136, 138, 141, 142], dittany [137], peppermint [110, 111, 135 137, 143], spearmint [136, 143145], common balm [110, 111, 146], allspice [25], fennel [147149], nutmeg [25, 137], caraway [139], cinnamon [137, 139, 150, 151], bay [137], dill [137], parsley [137], coriander [137, 144, 152], cumin [153, 154], garlic [25, 155157], hyssop [134, 140], and sarsaparilla [158160]. The main antioxidative compounds and types of compounds are listed in Tab. 3. Even though strong antioxidant activities of many plant extracts have been reported, the need for novel natural antioxidants is obvious, and industry continues to look for them. Kim et al. [161] studied the antioxidant activities of the methanol extracts of 180 oriental herbs during linoleic acid storage at 50 7C. Strong antioxidant activities were shown for 44 species. It was also established that the antioxidative properties of most herb extracts were greatly dependent on the extraction solvent used.

Tab. 3. Antioxidants isolated from herbs and spices. Species Rosemary Sage Oregano Thyme Ginger Turmeric Systematic names Rosemarinus officinalis (Labiatae) Salvia officinalis (Labiatae) Origanum vulgare (Labiatae) Thymus vulgaris (Labiatae) Zingiber officinale (Zingiberaceae) Substances and type of substances References

Carnosic acid, carnosol, rosmarinic acid, rosmanol [23, 56, 63] Carnosol, carnosic acid, rosmanol, rosmarinic acid [65, 76] Derivatives of phenolic acids, flavonoids, tocopherols Thymol, carvacrol, p-cumene-2,3-diol, biphenyls, flavonoids Gingerol-related compounds, diarylheptanoids [86, 88, 90] [99, 100] [104] [109] [93, 115, 116] [120, 121] [95] [95] [123] [134] [146] [128, 129]

Curcuma domestica (Zingiberaceae) Curcumins Rosmarinic acid, carnosol, carvacrol, thymol Phenolic amides, flavonoids Capsaicin

Summer savory Satureja hortensis (Labiatae) Black pepper Red pepper Chilli pepper Clove Marjoram Common balm Licorice Piper nigrum (Piperaceae) Capsicum annuum (Solanaceae)

Capsicum frutescence (Solanaceae) Capsaicin, capsaicinol Eugenia caryophyllata (Caryophyllaceae) Majorana hortensis (Labiatae) Melissa officinalis (Labiatae) Glycyrrhiza glabra (Leguminosae) Eugenol, gallates Flavonoids Flavonoids Flavonoids, licorice phenolics

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 substrate used in the evaluation. Chipault et al. [7, 8] reported that rosemary and sage were remarkably effective antioxidants and that oregano, thyme, nutmeg, mace and turmeric also retarded the oxidation of lard. In an oilin-water emulsion, clove showed extremely high antioxidant activity, and to a lesser degree did turmeric, allspice, mace, rosemary, nutmeg, ginger, cinnamon, oregano, savory and sage. Some of the results, obtained later, on the relative antioxidant activity of various herbs and spices in different substrates are summarized in Tab. 4.

10 Comparison of the antioxidative effects of various herbs and spices

A large number of reports concerned with antioxidative activity of herbs and spices have been published. Comparison of the results is complicated by several factors. Different activities are found for whole plant material and the extracts. Antioxidant activity varies according to the country in which the plant was grown [25]. The early research recognized also that the antioxidative activity of herbs and spices, or of their extracts, depends on the

Tab. 4. Relative antioxidative effectiveness (RAE) of spice extracts. Extraction method Commercial product Commercial product Substrate, conditions Analytical method RAE Rosemary . sage . nutmeg Rosemary . sage . marjoram . mace . black pepper Sage . rosemary References [162] [163]

Lecithin emulsion, daylight, PV, TBARS, AV room temperature, 26 days Lard, 50 7C PV, AV

Suspension in peanut oil, followed by molecular distillation

Chicken fat, 90 7C

O2 uptake

[55]

Oleoresin commercial Methyl linoleate, 100 7C product Methanol Lard, 75 7C

Gas chromatography

Sage . deodorized rosemary . untreated rosemary Oregano . thyme . dittany . majoram . spearmint . lavendel . basil Summer savory . peppermint . common balm . spearmint . oregano . common basil Sage . thyme . oregano . juniper Clove . oregano . cinnamon = marjoram . caraway Ginger . clove . pepper . cinnamon . fennel Ginger . cinnamon . clove . pepper . fennel Caraway . wild majoram . cinnamon Sage . basil . thyme . ginger Ginger . basil = thyme

[164]

PV

[136]

Ethanol

Triacylglycerols of sunflower oil, 100 7C

PV

[110]

Ethanol Methanol

Low-erucic rapeseed oil, 60 7C, 23 days Methanol

PV Scavenging effect of DPPH radical, H2O2 and O22 PV, AV PV, AV TBARS TBARS PV

[75] [139]

Dichloromethane Dichloromethane Ethanol Ethanol Ethanol

Lard Peanut oil Minced chicken meat, 4 and 18 7C Raw pork meats, pretreated with NaCl, 4 and 18 7C Microwave-cooked pork patties treated with NaCl, 18 7C

[150] [150] [22] [22] [22]

PV, peroxide value; AV, aldehyde value; TBARS, thiobarbituric acid-reactive substances.

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Eur. J. Lipid Sci. Technol. 108 (2006) 776793 The observation that the more polar antioxidants are more active in pure lipids, and non-polar antioxidants are most active in a polar substrate, e.g. oil-in-water emulsion, and for which the term polar paradox has been introduced [71], may at least partially explain the variation of antioxidant activity for different herbs and spices in different foods. Therefore, the necessity of evaluation of the antioxidative activity in heterogeneous model systems and in the actual food products prior to practical use should be emphasized. A three-step procedure for evaluation of spices was suggested [165]: (a) determination of the radical-scavenging activity using ESR spectroscopy, (b) tests in model systems, and (c) final tests in food storage experiments. It was also found that there was a reduced antioxidant activity in extracts prepared from an equivalent amount of spice as opposed to that prepared from the whole spice, confirming that a wide range of compounds are important as antioxidants in the plant material, which further may act synergistically [7, 29]. The ESR method based on a hydroxyl-generating system showed that the presence of spice extracts (basil, marjoram, hyssop, summer savory, oregano, sage) diminished the ESR signal, indicating that compounds in the extract compete efficiently for the hydroxyl radicals [138]. The relatively high activity and hence small selectivity for all of the spices could be due to the fact that the hydroxyl radicals are very aggressive. Beddows et al. [166] studied the ability of available herb and spice extracts to preserve a-tocopherol in sunflower oil during heating at 85105 7C. The authors found that rosemary, thyme, turmeric, sage, oregano and cumin extracts (0.2%) delayed rancidity and preserved a-tocopherol. Besides, with thyme, rosemary and sage extracts, the increase in the preservation of a-tocopherol was directly related to the concentration of the herb extract and was quite effective, even at 0.01%. Leafy spices like thyme, marjoram, basil, sage, and summer savory all showed pro-oxidative activity for foods exposed to light [29, 167, 168], while the same food stored in the dark confirmed the antioxidative effect of the spices. The effect of photosensitization of chlorophyll present in spices may be more important than the effect of the antioxidants for food exposed to light. However, the balance between photosensitization and antioxidative effect is very delicate and may depend on co-extraction of carotenoids, which may act as singlet oxygen quenchers [169]. The essential oils from a number of herbs and spices were also studied for antioxidant activity, e.g. oregano [87, 137, 152, 170172], rosemary [137, 152, 173176], sage [152,

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173, 176, 177], clove [152, 173, 178], coriander [137, 152], cumin [137, 173, 179], fennel [137, 180], thyme [173, 178 183], marjoram [137, 174], laurel [152, 180], caraway [137, 173], common balm [184], and summer savory [185]. The synergistic effect of various herbs and spices with synthetic antioxidants [23], with citric acid [7] and with atocopherol [54, 186] has been investigated. Synergism has been observed between different spices and BHA [187], the effect being most pronounced with sage, rosemary and mace. Basaga et al. [35] reported that rosemary extract and BHT, when added as mixtures of 75 : 25, 50 : 50 and 25 : 75, had a synergistic effect on preventing soybean oil oxidation. A combination of 0.064% rosemary extract, 0.061% sage extract and 0.041% citric acid has been recommended for use in flaxseed oil before deep-fat frying [188]. The activities of spice and herb extracts could be increased by synergistic activity of other harmless antioxidants such as soy, rapeseed or sunflower lecithin, ascorbyl palmitate, ammonium or amino acid salts of phosphatic acids, amino acids, and lower peptides. The activities of the extracts are higher in food containing protein, as sulfur and amino groups of the polypeptide chains interact with hydroperoxides, thus decreasing the free radical level [189].

11 Concluding remarks
The use of spices and herbs as antioxidants is a promising alternative to the use of synthetic antioxidants. In spite of scientific documentation of the antioxidative effect of many spices and herbs, today it is mainly extracts from leaves of rosemary and sage that are used as antioxidative spice additives. A range of commercial products containing extracts of rosemary are available; some of the products are water dispersible, others are oil soluble, and in order to exploit the synergistic effect, some of them are combined with tocopherols. The stabilization effect of the additives depends strongly on the composition of the complex lipid system and of the lipid-containing foods, as well as on the conditions of processing and storage (temperature, irradiation, partial oxygen pressure). That is why, prior to practical use in the food industry, any spice or spice extract should accordingly be tested in the actual food under realistic conditions. In experiments with foods, spices should be evaluated at concentrations that are accepted by the senses and with all interfering compounds present. It is important to mention that it is difficult to compare the antioxidant activities of herbs and spices because of lack of reference method(s) for comparing this activity. www.ejlst.com

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[16] M. Lacroix, W. Smoragiewicz, L. Pazdernik, K. I. Kone, K. Krzystyniak: Prevention of lipid radiolysis by natural antioxidants from rosemary (Rosmarinus officinalis L.) and thyme (Thymus vulgaris L.). Food Intern. 1997, 30, 457462. [17] Y. El-Shattory, S. M. Aly, S. F. Hamed, K. Schwarz: Effect of rosemary leaves on autoxidation of purified corn and soybean triacylglycerols. Egypt J Chem. 2005, 48, 155167. [18] E. Capecka, A. Mareczek, M. Leja: Antioxidant activity of fresh and dry herbs of some Lamiaceae species. Food Chem. 2005, 93, 223226. [19] A. Palitzsch, H. Schulte, F. Metzl, H. Baas: Effect of natural spices, spice extracts, essential oils, extraction residues, and synthetic antioxidants on the decomposition of pork fat and model lipids. I. Effect of natural spices and spice extracts on pork fat. Fleischwirtschaft 1969, 49, 13491354. [20] A. Palitzsch, D. Krizanec, Z. Dikanovic-Lucan: The antioxidant properties of spices in dry-fermented sausages. Fleischwirtschaft. 1993, 73, 670672. [21] U. Gerhardt, T. Bhm: Redox behavior of spices in meat products. Fleischwirtschaft 1980, 60, 15231526. [22] S. S. L. Abd El-Alim, A. Lugasi, J. Hovari, E. Dworschak: Culinary herbs inhibit lipid oxidation in raw and cooked minced meat patties during storage. J Sci Food Agric. 1999, 79, 277285. [23] S. J. Bishov, Y. Masuoka, J. G. Kapsalis: Antioxidant effect of spices, herbs and protein hydrolyzates in freeze-dried model systems: Synergistic action with synthetic phenolic antioxidants. J Food Process Preserv. 1977, 1, 153166. [24] B. Al-Jalay, G. Blank, B. McConnel, M. Al-Khayat: Antioxidant activity of selected spices used in fermented meat sausages. J Food Protect. 1987, 50, 2527. [25] H. L. Madsen, G. Bertelsen: Spices as antioxidants. Trends Food Sci Technol. 1995, 6, 271277. [26] F. Shahidi, R. B. Pegg, Z. O. Saleemi: Stabilization of meat lipids with ground spices. J Food Lipids. 1995, 2, 145153. [27] M. Huisman, H. L. Madsen, L. H. Skibsted, G. Bertelsen: The combined effect of rosemary (Rosmarinus officinalis L.) and modified atmosphere packaging as protection against warmed over flavour in cooked minced meat. Z Lebensm Unters Forsch. 1994, 198, 5759. [28] M. Tsimidou, E. Papavergou, D. Boskou: Evaluation of oregano antioxidant activity in mackerel oil. Food Res Intern. 1995, 28, 431433. [29] H. L. Madsen, B. Sorensen, L. H. Skibsted, G. Bertelsen: The antioxidative activity of summer savory (Satureja hortensis L.) and rosemary (Rosmarinus officinalis L.) in dressing stored exposed to light or in darkness. Food Chem. 1998, 63, 173180. [30] D. Bertelli, M. Plessi, F. Miglietta: Effect of industrial microwave treatment on antioxidant activity of herbs and spices. Ital J Food Sci. 2004, 16, 97103. [31] U. Gerhardt, A. Schrter: Antioxidative Wirkung von Gewrzen. Gordian. 1983, 83, 171172; 174176. [32] M. Rac, B. Ostric: Les proprietes antioxigene du romarin. Rev Franc Corps Gras. 1955, 2, 796803. [33] K. Nozaki: Antioxidant activity of rosemary. N Food Ind (Japan). 1989, 31, 2731. [34] O. I. Aruoma, J. P. E. Spencer, R. Rossi, R. Aeschbach, A. Khan, N. Mahmood, A. Munoz, A. Murcia, J. Butler, B. Halliwell: An evaluation of the antioxidant and antiviral action of extracts of rosemary and Provencal herbs. Food Chem Toxicol. 1996, 34, 449456. [35] H. Basaga, C. Tekkaya, F. Acikel: Antioxidative and free radical scavenging properties of rosemary extract. Food Sci Technol. 1997, 30, 105108.

A determination of the reduction potential of key compounds would be of interest for determining which of the spice antioxidants can regenerate the tocopherols. The problems encountered because photosensitizing chlorophyll co-extraction from the spice makes the food product sensitive to light also needs further investigation.

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