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Nedyalka V. Yanishlieva a Emma Marinova a Jan Pokorny ´ b a 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 Natural antioxidants from herbs and spices 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. This review presents the results on stabilization of lipids and lipid- containing 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, nut- meg, 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 respon- sible 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 [1–6]. Since the early work of Chipault et al. [7–9] 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 [10–13]. 2 Ground herbs and spices In the evaluation of spices, some investigations have been carried out using the whole spice [14–18]. Tab. 1 illustrates the importance of the substrate used for eval- uating the antioxidative activity of the additives. Rose- mary 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 ac- tivity [20–22]. 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. Gin- ger 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 addi- tion 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]. 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 776 DOI 10.1002/ejlt.200600127 Eur. J. Lipid Sci. Technol. 108 (2006) 776–793 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com Review Article
Transcript
Page 1: Antioxidantes Naturales de Hierbas y Especies

Nedyalka V. Yanishlievaa

Emma Marinovaa

Jan Pokornyb

a Institute of Organic Chemistry,Bulgarian Academyof Sciences,Sofia, Bulgaria

b Faculty of Food andBiochemical Technology,Prague Institute of ChemicalTechnology,Prague, Czech Republic

Natural antioxidants from herbs and spices

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 spicesare one of the most important targets to search for natural antioxidants from the pointof view of safety. This review presents the results on stabilization of lipids and lipid-containing foods with different herbs and spices (ground materials or extracts) andreports 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, nut-meg, garlic, coriander, etc. Among the herbs of the Labiatae family, rosemary has beenmore 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 manyresearch groups as potential antioxidants.

Keywords: Herbs, spices, natural antioxidants, antioxidant activity.

1 Introduction

Lipid oxidation occurring in food products is one ofthe major concerns in food technology. It is respon-sible for rancid odors and flavors of the products, witha consequent decrease in nutritional quality and safetycaused by the formation of secondary, potentiallytoxic compounds. The problem of ensuring a highquality of lipids and lipid-containing products andprolonging their storage time is directly associatedwith their optimum stabilization by addition of suitableantioxidants. This is very important to human healthprotection and also economically important. There is agrowing interest in natural antioxidants found in plantsbecause of the world-wide trend toward the use ofnatural additives in food and cosmetics. Herbs andspices are one of the most important targets to searchfor natural antioxidants from the point of view of safety[1–6].

Since the early work of Chipault et al. [7–9] who haveexamined more than 70 spices and herbs, the interest inthe antioxidative activity of spices has increased and ledto an increase in information about the compounds andmechanism involved [10–13].

2 Ground herbs and spices

In the evaluation of spices, some investigations havebeen carried out using the whole spice [14–18]. Tab. 1illustrates the importance of the substrate used for eval-uating the antioxidative activity of the additives. Rose-mary and sage were the most effective antioxidants inlard [7, 19] and both spices were found to have a lowredox potential in sausages indicating antioxidative ac-tivity [20–22]. However, in an oil-in-water emulsion, clovewas the most effective spice [8, 23, 24]. In general, thestabilization factors obtained for the spices in emulsionswere several times greater than those in lard, indicating ahigher efficiency against oxidation in the emulsion [25].

Shahidi et al. [26] reported that the antioxidative activity ofground clove, ginger, oregano, sage and thyme in meatlipids was concentration dependent, but clove was themost effective, followed by sage and then rosemary. Gin-ger and thyme exerted the weakest effect. Dried leaves ofrosemary added to cooked pork meat balls retarded thedevelopment of warmed over flavor (WOF) during coldstorage [27]. Tsimidou et al. [28] found that 1% oreganowas equivalent to 200 ppm butylated hydroxyanisol (BHA)in controlling oxidation of mackerel oil. For an oil-in-wateremulsion, addition of 0.15% of dried leaves of summersavory, or more significantly of rosemary, resulted in asignificantly better antioxidative protection than the addi-tion of 80 ppm propyl gallate (PG) [29]. The industrialtreatment with microwaves of black pepper, basil andsage did not modify the antioxidant properties of theseherbs and spices [30].

Correspondence: Nedyalka V. Yanishlieva, Institute of OrganicChemistry, 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: [email protected]

776 DOI 10.1002/ejlt.200600127 Eur. J. Lipid Sci. Technol. 108 (2006) 776–793

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com

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Eur. J. Lipid Sci. Technol. 108 (2006) 776–793 Natural antioxidants from herbs and spices 777

Tab. 1. Relative antioxidative effectiveness (RAE) of spices and herbs, evaluated as whole plant material in different sub-strates.

Spice, herb, tea Substrate RAE Refer-ences

Marjoram, nutmeg, white pepper, rosemary,sage, coriander, black pepper

Lard Rosemary . sage . nutmeg . whitepepper . marjoram

[19]

32 different Lard Rosemary . sage . oregano. nutmeg . thyme

[7]

19 different Oil-in-water-emulsion Clove . cinnamon . sage . mace. oregano

[23]

32 different Oil-in-water-emulsion Clove . turmeric . allspice . mace. rosemary

[8]

10 different Oil-in-water-emulsion Clove . allspice . cinnamon. nutmeg . ginger

[24]

Allspice, red paprika, savory, marjoram,black pepper, white pepper, coriander

Sausage, water Allspice . red paprika . savory. marjoram . black pepper

[20]

15 different Sausage, water Sage . rosemary . paprika. marjoram . aniseed

[21]

12 different Ground chicken meat Marjoram . caraway . peppermint. clove

[22]

The influence of the type of food system on the stabiliza-tion factor of different spices is presented in Tab. 2 [31].

Tab. 2. Stabilization factor, F§, of different herbs andspices in four foods [31].

Substrate Lard Oil-in-wateremulsion

Mincedpork meat

Mayon-naise

Storage temperature [7C] 99 63 25 20Spice, concentration

in fat [%]0.2 0.1 0.25 0.2

Clove 1.8 16.7 ,5.3 1.4Rosemary 17.6 10.2 ,5.3 2.2Sage 14.2 7.8 ,5.3 2.4Oregano 3.8 7.9 ,7.2 8.5Summer savory 1.6 7.9 1.0 1.5Thyme 3.0 6.8 6.0 1.8Ginger 1.8 8.8 1.3 1.0Curcuma 2.9 15.9 4.5 0.9Nutmeg 3.1 9.2 5.3 0.9

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

3 Rosemary (Rosmarinus officinalis L.)

Rosemary is one of the most effective spices widely usedin food processing. It is the only spice commerciallyavailable for use as an antioxidant in Europe and theUnited States.

The first use of an extract of rosemary leaves as an anti-oxidant was reported by Rac and Ostric-Matijasevic [32].Antioxidant properties of rosemary have been well docu-mented [33–42]. Rosemary was considered as both lipidantioxidant and metal chelator [33]. Rosemary extractswere found also to scavenge superoxide radicals [35].

Many different solvents have been used for the extractionof the antioxidative compounds [43–47]. Chang et al. [43]extracted rosemary leaves with hexane, benzene, ethylether, chloroform, ethylene dichloride, dioxane andmethanol. The extracts (0.02%) were tested during oxi-dation of lard at 60 7C in the dark. It was established thatthe greatest antioxidant activity was located in the meth-anol extract. Marinova et al. [45], Chen et al. [46] andPokorny et al. [47] found that the hexane extracts fromrosemary were better antioxidants for lard [45, 46], rape-seed and sunflower oils [47] than the methanol [46] orethanol [45, 47] extracts. In rapeseed oil, hexane extractsfrom rosemary and sage were also more efficient thanethyl acetate or acetone extracts [48]. The antioxidativeeffect of rosemary ethanol extract on butter has also beenstudied [49].

Rosemary antioxidants were found suitable for deep-fry-ing of edible oils [50], especially in the presence of ascor-byl palmitate [51]. Reblova et al. [52] investigated theeffect of acetone and ethyl acetate extracts on thechanges in rapeseed oil and in an oil containing poly-

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siloxanes during frying of potatoes. The authors estab-lished that the rosemary extracts inhibited the formationof polar substances and polymers and the decompositionof polyunsaturated triacylglycerols.

Trojakova et al. [53] reported that rosemary efficientlyprotects tocopherols naturally present in rapeseed oil.Wada and Fang [54] observed a strong synergistic effectbetween rosemary extract (0.02%) and a-tocopherol(0.05%) in sardine oil at 30 7C and in frozen-crushed meatmodels. The authors suggested that rosemary extractfunctions as a hydrogen atom donor regenerating the a-tocopheryl radical to a-tocopherol. A very pronouncedsynergistic effect was seen between citric acid androsemary extract [7].

Concurrent with the evaluation of rosemary extracts asantioxidants to inhibit lipid oxidation, research was alsofocused on isolation, identification and testing of theactive compounds contained in the extracts. In a study of16 compounds isolated from rosemary, Bracco et al. [55]concluded that the antioxidant activity of rosemaryextracts is primarily related to carnosol 1 and carnosicacid 2 (Fig. 1). Nakatani and Inatani [56] identified rosma-nol 3 (Fig. 1) and carnosol and found that both were moreeffective than a-tocopherol, BHT and BHA. The sameauthors [57] isolated also rosmadial 4 from rosemary(Fig. 1).

Several other antioxidative diterpenes such as epiros-manol 5 and isorosmanol 6 [58], rosmaridiphenol 7 [59]and rosmariquinone (RQ) 8 [60] have been reported tocontribute to the antioxidant activity of rosemary extracts(Fig. 1). During the storage and extraction of rosemary,carnosic acid is partially converted either into carnosol orinto other diterpenes such as rosmanol [55, 61, 62].

Rosmarinic acid (RA) 9 (Fig. 1) was reported by Gerhardtand Schröter [63] to be the second most frequentlyoccurring caffeic acid ester, following chlorogenic acid,and to have antioxidant activity equivalent to that of caf-feic acid. The authors detected RA in rosemary, balm,sage, thyme, oregano, marjoram, peppermint, and for thefirst time in basil. Recently, Bano et al. [64] studied thedistribution of phenolic diterpenes, flavones and RA dur-ing the development of leaves, flowers, stems and rootsof rosemary.

There are many data in the literature concerning the anti-oxidative properties of the individual compounds isolatedfrom rosemary. Briskorn and Domling [65] showed thatcarnosic acid and carnosol were as effective as BHT andthat their effectiveness was concentration dependent.The authors noted that the activity of both compoundswas due to the cooperation of their ortho phenolic groupswith their isopropyl group.

Fig. 1. Formulae of the antioxidativelyacting compounds I.

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It was also reported that rosmanol had greater antioxidantactivity than carnosol [56], with carnosic acid being morepotent than carnosol [61, 66]. In soybean oil, carnosicacid was found to be more active than BHTand BHA, butless active than TBHQ. Carnosic acid and carnosolshowed the ability to chelate iron and were effective radi-cal scavengers of peroxyl radicals [67].

Houlihan et al. [59] found rosmaridiphenol to be moreactive than BHA in lard and equivalent to BHT in this testsystem. They reported also that RQ was superior to BHAand equivalent to BHT in controlling the oxidation of lard[60]. RQ has been shown to have good antioxidant activ-ity also in soybean oil [68]. Hall et al. [69] proved that RQacted as a hydrogen-donating antioxidant. Isorosmanoland epirosmanol showed high activity in both lard andlinoleic acid [58]; in lard, they were four times more activethan BHA and BHT. Nakamura et al. [70] reported that RAexhibited a significantly higher superoxide-scavengingactivity than ascorbic acid.

As far as the complex food systems are concerned, it isimportant to clarify the antioxidative behavior not only inbulk oil, but also in oil-in-water emulsions [71–73], as wellas in microsomal and liposomal systems [67]. Frankel etal. [71] reported that in bulk corn oil, rosemary extract,carnosic acid and RA were significantly more active thancarnosol. In contrast, in corn oil-in-water emulsion, therosemary compounds were less active than in bulk oil,and in the rosemary extract, carnosic acid and carnosolwere more active than RA. The decreased antioxidantactivity of the polar hydrophilic rosemary compounds inthe emulsion system may be explained by their interfacialpartitioning into water, thus becoming less protective thanin the bulk oil system [71]. Carnosol and carnosic acidwere powerful inhibitors of lipid peroxidation in micro-somal and liposomal systems [67].

4 Sage (Salvia officinalis L.)

Salvia officinalis L., commonly known as sage, is used infoods for flavoring and seasoning. It was found that, alongwith rosemary, it has the best antioxidant activity amongthe numerous herbs and spices tested [7, 8]. Its extractsare also well known as efficient antioxidants [74–79].

Since methanol and ethanol were found to be the mostsuitable solvents for extraction of antioxidants from plantmaterials, a number of publications have dealt with furtherpurification of the alcohol extracts. Vacuum steam dis-tillation [43] or molecular distillation [55] are recom-mended for use on production scale.

Since rosemary and sage belong to the Labiatae family, itis not surprising to find the same antioxidants in both

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 andcarnosic acid can be found in sage, as well as in otherLabiatae plant extracts; in most cases, the compoundsare believed to be artifacts from the extraction proce-dures [63, 65].

The main antioxidative effect of sage was reported torelate 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-b-glucopyranoside 11 [84], 6-O-caffeoyl-b-D-fructofur-anosyl-(2?1)-a- D -glucopyranoside 12 and 1-O-caffeoyl-b-D-apiofuranosyl-(1?6)-b-glucopyranoside 13 [85](Fig. 2).

Lu and Foo [83] studied the antioxidant activity of flavo-noids and phenolic acids isolated from sage, using threedifferent test methods, namely DPPH free radical, super-oxide anion radical, generated from the xanthine/xanthineoxidase system, and reduction of the phosphomolybde-num complex. The authors found that the antioxidant ac-tivity of the flavonoids was variable and that those with acatechol B-ring (luteolin glycosides) were more activethan those without (apigenin glycosides).

5 Oregano (Oreganum vulgare L.)

Oregano is very often used as a spice and its flavor ishighly favorable to consumers all over the world. It isvalued also for its antimicrobial and antioxidant proper-ties.

Dry oregano, as well as extracts obtained by using sol-vents of different polarity (hexane, dichloromethane,methanol) have been tested as retarders of lipid oxidationin model systems or in real food products [7, 9, 28, 86].Abdalla and Roozen [77] reported that oregano acetoneextract 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 Origanumdictamnus were also investigated [87–89].

The water-soluble fraction of the methanol extract of ore-gano leaves was purified with polyamide chromatographyto give five polar compounds [90, 91] – RA, caffeic acid14, protocatechuic acid 15, a new glucoside of proto-catechuic acid 16, and a derivative of RA, 2-caffeoyloxy-3-[2-(4-hydroxybenzyl)-4,5-dihydroxy] phenylpropionicacid 17 (Fig. 3). In the ethyl ether layer from the ethanolextract, Vekiari et al. [86, 92] identified four flavonoids –

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Fig. 2. Formulae of the antioxidatively act-ing compounds II.

Fig. 3. Formulae of the antioxidativelyacting compounds III.

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apigenin 18, eriodictyol 19, dihydroquercetin 20, anddihydrokaempherol 21. In the hexane extract a-, b-, g-and d-tocopherols were found [88] (Fig. 3).

The essential oil obtained from oregano contained carva-crol 22 and thymol 23 [87, 93] (Fig. 3). According toLagouri et al. [87], the antioxidative effect of oregano maybe related to the presence of these isomers. Yanishlievaet al. [94] established that thymol and carvacrol differed inthe mechanism of their inhibiting action at room temper-ature, which depended on the character of the lipid me-dium. Thymol was a better antioxidant in triacylglycerolsof sunflower oil than in triacylglycerols of lard.

6 Thyme (Thymus vulgaris L.)

Thyme comes originally from the regions around theMediterranean and is used as cough medicine. It has alsobeen commonly used as one of the culinary herb spicesfor adding flavor and deodorizing.

The phenolic monoterpenes in thyme, thymol and carva-crol, are the primary compounds that contribute to thecharacteristic aroma of its essential oil [95]. They are alsoknown to inhibit lipid peroxidation [94, 96–98]. p-Cumene-2,3-diol 24 (Fig. 4) isolated from thyme is also a

strong antioxidant [97]. The antioxidative effect of thymeethanol extract is associated with the high content ofcarvacrol and thymol [98].

Antioxidative activity was found in the weakly acidic frac-tion, which was repeatedly purified by chromatography togive five new diphenyldimers of thymol and carvacrol 25–29 [99] (Fig. 4) and highly methoxylated flavonoids 30–32[100] (Fig. 4).

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

The rhizome of the popular ginger species, Zinger offici-nale, is currently widely used as a spice and food sea-soning due to its sweet aroma and pungent taste. It hasbeen known to have antioxidant activity [101, 102]. It hasbeen found that the extracts of fresh ginger showed ahigher activity than that of stored ginger [103].

The non-volatile fraction of the dichloromethane extractof dried ginger was purified by CC and HPLC to yieldmore than 30 compounds, 16 of which were new [104].These compounds were structurally classified into gin-gerol-related compounds and diarylheptanoids (com-pounds 33–46, Fig. 5), and their structure-antioxidant

Fig. 4. Formulae of the anti-oxidatively acting compounds IV.

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Fig. 5. Formulae of the anti-oxidatively acting compounds V.

relationship in an aqueous ethanolic solution of linoleicacid was examined [104, 105]. The pungent components,gingerol 33, shogaol 34 and zingerone 35, were reportedto show high activity [106].

The dried rhizome of turmeric is widely used as a spice, asa coloring agent and as a folk medicine. The yellow pig-ment curcumin 46 and the curcumin derivatives 47–56(Fig. 6) are known to possess potent antioxidant activity[104–106]. Curcumin suppressed the oxidation of methyllinoleate in organic homogeneous solution and aqueousemulsions, soybean phosphatidylcholine liposomalmembranes and rat liver homogenate induced by free

radicals [107]. A mechanism for the dimer production hasbeen proposed and its relation to curcumin’s antioxidantactivity has been discussed [108]. The results indicatedthat the dimer is a radical-terminating product formedduring the initial stage of the process [108].

Matsuda and Jitoe [109] reported that the antioxidant ac-tivity of cassmunins A–C was stronger than that of curcu-min, and their antiflammatory activity was also strongerthan that of curcumin.

Jitoe et al. [101] studied the relationship between theantioxidant activity of nine tropical ginger extracts and

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Fig. 6. Formulae of the antioxidativelyacting compounds VI.

their curcuminoid quantities in a linoleic acid-ethanolsystem. The data indicated that the antioxidant activitiesof the ginger extracts were greater than that estimatedfrom the quantity of curcuminoid found in the extracts.Obviously, there is a synergism between the compoundspresent in the extracts.

8 Summer savory (Satureja hortensis L.)

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

Yanishlieva and Marinova [110] established that the etha-nol extract of the spice exhibited a good antioxidativeeffect in triacylglycerols of sunflower oil at 100 7C, as wellas in commercial sunflower oil [111]. The effect of theextract in lard is stronger at room temperature than at100 7C [112].

Addition of 0.1–0.5% of the ethanol extract of summersavory to sunflower oil decreased the oxidative and ther-mal changes in it during simulated deep-fat frying [113].The effect of ca. 200 ppm of freeze-dried methanolextract of summer savory, added to an oil-in-water emul-

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sion dressing, was comparable to the effect of PG [29].The antioxidative effect found for dark storage changedto a pro-oxidative effect during light exposure (850 lx). Thechlorophyll present in summer savory is believed to haveacted as an efficient sensitizer causing an acceleration ofthe oxidation process [29].

Dorman and Hiltunen [114] characterized the antioxidantproperties of an acidified aqueous methanol extract fromcommercially available summer savory. The authorsfound that the ethyl acetate-soluble subfraction of thecrude methanol extract was the most effective as anti-oxidant.

Antioxidative compounds isolated from summer savoryare RA [115], carnosol and carnosic acid [116], carvacroland thymol in the essential oil [93, 117]. Portuguese sav-ory oil does not contain thymol [118].

9 Other herbs and spices

Supercritical carbon dioxide extracts of ground blackpepper (Piper nigrum L.) have been found superior in re-ducing lipid oxidation of cooked ground pork [119]. Theantioxidative activity of black pepper can, at least par-tially, be ascribed to the presence of glycosides of theflavonoids kaempherol, rhamnetin and quercetin [120], aswell as to the phenolic amides 57–61 [121] (Fig. 7).

Chili pepper (Capsicum frutescence L.) and red pepper(C. annum L.) contain capsaicin 62 (Fig. 7), a pungentprinciple showing significant antioxidative properties. Anew antioxidant, capsaicinol 63 (Fig. 7), was isolated fromchili pepper [95]. Marcus et al. [122] reported the changein antioxidant content in red pepper (paprika) as a func-tion of ripening and some technological factors.

Fig. 7. Formulae of the anti-oxidatively acting compounds VII.

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Gallic acid 64 and eugenol 65 (Fig. 7) have been identifiedas the major active components in clove (Eugenia car-yophyllata) [123]. It has been established that isoeugenol66 (Fig. 7), more rarely found in nature, exhibited higherantioxidative efficiency than eugenol during methyl oleateoxidation [124] and lard and sunflower oil oxidation [125].Eugenol and isoeugenol have also an inhibiting effect onthe peroxidation of lecithin induced by the Fe21-H2O2

system [126].

Extracts of licorice (Glycyrrhiza glabra L.) also pos-sess antioxidant activity [127, 128]. The antioxidanteffect of licorice phenolics is well known [129]. Gor-don and An [128] isolated eight purified flavonoidsfrom the solvent extracts of licorice and studied theirantioxidant effectiveness in lard at 100 7C. Theauthors supposed a synergistic effect of the flavonoidmixture that may be responsible for the high activityobserved.

Different flavonoids were also isolated from the extract ofthe sage Salvia nemorosa L. [130], an aromatic perennialherb of the southern European region, and from Anthris-cus sylvestris [131], a Serbian plant species used in folkmedicine and in salad dressing. The flavonoids, andespecially flavonoid glycosides, can be found in nearly allherbs and spices tested [132].

The antioxidant extracts prepared from the seeds of theAfrican spice Aframomum danielli were more effectivethan 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, 134–140], basil [63, 110, 111, 136,138, 141, 142], dittany [137], peppermint [110, 111, 135–137, 143], spearmint [136, 143–145], common balm [110,111, 146], allspice [25], fennel [147–149], 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, 155–157], hyssop [134, 140],and sarsaparilla [158–160].

The main antioxidative compounds and types of com-pounds are listed in Tab. 3.

Even though strong antioxidant activities of many plantextracts have been reported, the need for novel naturalantioxidants is obvious, and industry continues to look forthem. Kim et al. [161] studied the antioxidant activities ofthe methanol extracts of 180 oriental herbs during linoleicacid storage at 50 7C. Strong antioxidant activities wereshown for 44 species. It was also established that theantioxidative properties of most herb extracts weregreatly dependent on the extraction solvent used.

Tab. 3. Antioxidants isolated from herbs and spices.

Species Systematic names Substances and type of substances References

Rosemary Rosemarinus officinalis (Labiatae) Carnosic acid, carnosol, rosmarinic acid, rosmanol [23, 56, 63]

Sage Salvia officinalis (Labiatae) Carnosol, carnosic acid, rosmanol, rosmarinic acid [65, 76]

Oregano Origanum vulgare (Labiatae) Derivatives of phenolic acids, flavonoids,tocopherols

[86, 88, 90]

Thyme Thymus vulgaris (Labiatae) Thymol, carvacrol, p-cumene-2,3-diol, biphenyls,flavonoids

[99, 100]

Ginger Zingiber officinale (Zingiberaceae) Gingerol-related compounds, diarylheptanoids [104]

Turmeric Curcuma domestica (Zingiberaceae) Curcumins [109]

Summer savory Satureja hortensis (Labiatae) Rosmarinic acid, carnosol, carvacrol, thymol [93, 115, 116]

Black pepper Piper nigrum (Piperaceae) Phenolic amides, flavonoids [120, 121]

Red pepper Capsicum annuum (Solanaceae) Capsaicin [95]

Chilli pepper Capsicum frutescence (Solanaceae) Capsaicin, capsaicinol [95]

Clove Eugenia caryophyllata(Caryophyllaceae)

Eugenol, gallates [123]

Marjoram Majorana hortensis (Labiatae) Flavonoids [134]

Common balm Melissa officinalis (Labiatae) Flavonoids [146]

Licorice Glycyrrhiza glabra (Leguminosae) Flavonoids, licorice phenolics [128, 129]

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10 Comparison of the antioxidative effectsof various herbs and spices

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

substrate used in the evaluation. Chipault et al. [7, 8]reported that rosemary and sage were remarkably effec-tive antioxidants and that oregano, thyme, nutmeg, maceand turmeric also retarded the oxidation of lard. In an oil-in-water emulsion, clove showed extremely high anti-oxidant activity, and to a lesser degree did turmeric, all-spice, mace, rosemary, nutmeg, ginger, cinnamon, ore-gano, savory and sage. Some of the results, obtainedlater, on the relative antioxidant activity of various herbsand spices in different substrates are summarized inTab. 4.

Tab. 4. Relative antioxidative effectiveness (RAE) of spice extracts.

Extraction method Substrate, conditions Analytical method RAE Refer-ences

Commercial product Lecithin emulsion, daylight,room temperature, 26 days

PV, TBARS, AV Rosemary . sage. nutmeg

[162]

Commercial product Lard, 50 7C PV, AV Rosemary . sage. marjoram . mace. black pepper

[163]

Suspension in peanutoil, followed bymolecular distillation

Chicken fat, 90 7C O2 uptake Sage . rosemary [55]

Oleoresin – commercialproduct

Methyl linoleate, 100 7C Gas chromatography Sage . deodorizedrosemary . untreatedrosemary

[164]

Methanol Lard, 75 7C PV Oregano . thyme . dittany. majoram . spearmint. lavendel . basil

[136]

Ethanol Triacylglycerols ofsunflower oil, 100 7C

PV Summer savory . peppermint. common balm. spearmint . oregano. common basil

[110]

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

PV Sage . thyme . oregano. juniper

[75]

Methanol Methanol Scavenging effect ofDPPH radical, H2O2

and O22

Clove . oregano . cinnamon= marjoram . caraway

[139]

Dichloromethane Lard PV, AV Ginger . clove . pepper. cinnamon . fennel

[150]

Dichloromethane Peanut oil PV, AV Ginger . cinnamon . clove. pepper . fennel

[150]

Ethanol Minced chicken meat,4 and –18 7C

TBARS Caraway . wild majoram. cinnamon

[22]

Ethanol Raw pork meats, pretreatedwith NaCl, 4 and –18 7C

TBARS Sage . basil . thyme. ginger

[22]

Ethanol Microwave-cooked porkpatties treated withNaCl, –18 7C

PV Ginger . basil = thyme [22]

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

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The observation that the more polar antioxidants are moreactive in pure lipids, and non-polar antioxidants are mostactive in a polar substrate, e.g. oil-in-water emulsion, andfor which the term “polar paradox” has been introduced[71], may at least partially explain the variation of anti-oxidant activity for different herbs and spices in differentfoods. Therefore, the necessity of evaluation of the anti-oxidative activity in heterogeneous model systems and inthe actual food products prior to practical use should beemphasized. A three-step procedure for evaluation ofspices was suggested [165]: (a) determination of theradical-scavenging activity using ESR spectroscopy,(b) tests in model systems, and (c) final tests in food stor-age experiments.

It was also found that there was a reduced antioxidantactivity in extracts prepared from an equivalent amount ofspice as opposed to that prepared from the whole spice,confirming that a wide range of compounds are importantas antioxidants in the plant material, which further mayact synergistically [7, 29].

The ESR method based on a hydroxyl-generating systemshowed that the presence of spice extracts (basil, mar-joram, hyssop, summer savory, oregano, sage) dimin-ished the ESR signal, indicating that compounds in theextract compete efficiently for the hydroxyl radicals [138].The relatively high activity and hence small selectivity forall of the spices could be due to the fact that the hydroxylradicals are very aggressive.

Beddows et al. [166] studied the ability of available herband spice extracts to preserve a-tocopherol in sunfloweroil during heating at 85–105 7C. The authors found thatrosemary, thyme, turmeric, sage, oregano and cuminextracts (0.2%) delayed rancidity and preserved a-toco-pherol. Besides, with thyme, rosemary and sage extracts,the increase in the preservation of a-tocopherol was di-rectly related to the concentration of the herb extract andwas quite effective, even at 0.01%.

Leafy spices like thyme, marjoram, basil, sage, and sum-mer savory all showed pro-oxidative activity for foodsexposed to light [29, 167, 168], while the same foodstored in the dark confirmed the antioxidative effect of thespices. The effect of photosensitization of chlorophyllpresent in spices may be more important than the effectof the antioxidants for food exposed to light. However, thebalance between photosensitization and antioxidativeeffect is very delicate and may depend on co-extractionof carotenoids, which may act as singlet oxygen quench-ers [169].

The essential oils from a number of herbs and spices werealso studied for antioxidant activity, e.g. oregano [87, 137,152, 170–172], rosemary [137, 152, 173–176], sage [152,

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 withsynthetic antioxidants [23], with citric acid [7] and with a-tocopherol [54, 186] has been investigated. Synergismhas been observed between different spices and BHA[187], the effect being most pronounced with sage,rosemary and mace. Basaga et al. [35] reported thatrosemary extract and BHT, when added as mixtures of75 : 25, 50 : 50 and 25 : 75, had a synergistic effect onpreventing soybean oil oxidation. A combination of0.064% rosemary extract, 0.061% sage extract and0.041% citric acid has been recommended for use inflaxseed oil before deep-fat frying [188].

The activities of spice and herb extracts could beincreased by synergistic activity of other harmless anti-oxidants such as soy, rapeseed or sunflower lecithin,ascorbyl palmitate, ammonium or amino acid salts ofphosphatic acids, amino acids, and lower peptides. Theactivities of the extracts are higher in food containingprotein, as sulfur and amino groups of the polypeptidechains interact with hydroperoxides, thus decreasing thefree radical level [189].

11 Concluding remarks

The use of spices and herbs as antioxidants is a promis-ing alternative to the use of synthetic antioxidants.

In spite of scientific documentation of the antioxidativeeffect of many spices and herbs, today it is mainlyextracts from leaves of rosemary and sage that are usedas antioxidative spice additives. A range of commercialproducts containing extracts of rosemary are available;some of the products are water dispersible, others are oilsoluble, and in order to exploit the synergistic effect,some of them are combined with tocopherols.

The stabilization effect of the additives depends stronglyon the composition of the complex lipid system and of thelipid-containing foods, as well as on the conditions ofprocessing and storage (temperature, irradiation, partialoxygen pressure). That is why, prior to practical use in thefood industry, any spice or spice extract should accord-ingly be tested in the actual food under realistic condi-tions. In experiments with foods, spices should be eval-uated at concentrations that are accepted by the sensesand with all interfering compounds present. It is importantto mention that it is difficult to compare the antioxidantactivities of herbs and spices because of lack of referencemethod(s) for comparing this activity.

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A determination of the reduction potential of key com-pounds would be of interest for determining which of thespice antioxidants can regenerate the tocopherols. Theproblems encountered because photosensitizing chloro-phyll co-extraction from the spice makes the food prod-uct sensitive to light also needs further investigation.

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[Received: June 5, 2006; accepted: August 4, 2006]

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