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ISSN 0003-6838, Applied Biochemistry and Microbiology, 2009, Vol. 45, No. 6, pp. 642–647. © Pleiades Publishing, Inc., 2009.Original Russian Text © T.A. Misharina, M.B. Terenina, N.I. Krikunova, 2009, published in Prikladnaya Biokhimiya i Mikrobiologiya, 2009, Vol. 45, No. 6, pp. 710–716.

642

To protect from infections and parasites and inresponse to stress, plants synthesize low molecular vol-atile terpenoids, the mixture of which is called essentialoils. Essential oils of many plants possess a strong andpleasant aroma and are also biologically active [1–3].Due to these properties, essential oils are actively usedin the medical and pharmaceutical industries, in aroma-therapy and cosmetology, and in the production of nat-ural food flavorings[3, 4]. As a rule, essential oils are acomplex mixture of organic substances with differentfunctional groups, mainly terpenoids. The compositionof essential oils determines their organoleptic proper-ties and biological activity including antioxidant [5–8].The study of individual components of different essen-tial oils has shown that many terpenes possess antirad-ical and antioxidant activity (AOA) and the activity ofcyclic monoterpene hydrocarbons with two doublebonds is comparable with AOA of phenol and

α

toco-pherol [9–11]. Thus,

α

-

and

γ

-terpinenes and sesquiter-pene hydrocarbons, including caryophyllene, inhibitedmethyl linoleate oxidation [10–13]. Sabinene,

α

-

and

γ

-

terpinenes and

α

- terpinolene are active donors ofhydrogen in reference to the 2,2-diphenyl-1-picrilhy-drazyl radical, which is used for the estimation of anti-radical activity [10, 14–16]. Citronellal, neral, andgeranial, which are included in many essential oils,possess antiradical activity [10, 14, 17, 18]. As a rule,antioxidant activity of essential oils is higher than fortheir individual components. This indicates the exist-ence of synergetic effects due to the complex multi-component composition of oils [15, 19, 20].

To estimate the antioxidant properties of substancesor their mixtures, many different methods are used. Itwas showed that the value of AOA significantlydepends on the method of its estimation, which is whythe literature data obtained by different methods arepractically incomparable. In addition, the antioxidantproperties of essential oils depend on the qualitativeand quantitative composition of systems under test [6,10, 13, 20, 21]. One of the simple and informativemethods of quantitative assessment of AOA is based oninhibition of the rate of lower aldehyde autooxidation,for example, hexanal, in the presence of antioxidantsubstances [7, 8, 20, 22]. This method has been usedsuccessfully for to estimate and compare the antioxi-dant properties of a number of essential oils [20, 22–25].

The aim here is to study and compare antioxidantproperties of 14 essential oils in the model system ofautooxidation of 2-hexenal, assess the influence of thecomposition of essential oils on their AOA, and to studythe changes in the composition of essential oils in theprocess of autooxidation in solutions and in pure forms.

METHODS

We studied fresh samples of essential oils of blackand white pepper (

Piper

nigrum L.), cardamom (

Elet-taria cardamomum

L.), nutmeg (

Myristica fragrans

Houtt.), mace (

Myristica

fragrans Houtt.), juniper berry(

Juniperus communis

L.), fennel seed (

Foeniculum vul-gare

Mill., var.

dulce

Thelling), caraway (

Carvum carvi

L.),

Antioxidant Properties of Essential Oils

T. A. Misharina, M. B. Terenina, and N. I. Krikunova

Emanuel Institute of Biochemical Physics, Russian Academy of Sciencesul. Kosygina 4, Moscow, 119991 Russia

e-mail: [email protected]

Received September 23, 2008

Abstract

—By the method of capillary gas-liquid chromatography, we studied the antioxidant properties and sta-bility during the storage of hexane solutions of 14 individual essential oils from black and white pepper (

Pipernigrum

L.), cardamom (

Elettaria cardamomum

L.), nutmeg (

Myristica fragrans

Houtt.), mace (

Myristica

fragransHoutt), juniper berry (

Juniperus communis

L.), fennel seed (

Foeniculum vulgare

Mill., var.

dulce

Thelling), cara-way (

Carvum carvi

L.), dry cinnamon leaves (

Cinnamomum zeylanicum

Bl.), marjoram (

Origanum majorana

L.),laurel (

Laurus

nobilis L.), ginger (

Zingiber officinale

L.), garlic (

Allium sativum

L.), and clove bud (

Caryophyllus aro-maticus

L.). We assessed the antioxidant properties by the oxidation of aliphatic aldehyde (trans-2-hexenal) intothe corresponding carbonic acid. We established that essential oils of garlic, clove bud, ginger and leaves of cin-namon have the maximal efficiency of inhibiting hexenal oxidation (80!–93%), while black pepper oil has the min-imal (49%). Antioxidant properties of essential oils with a high content of substituted phenols depended poorly ontheir concentrations in model systems. We studied the changes in the composition of essential oils during the stor-age of their hexane solutions for 40 days in light and compared it with the stability of essential oils stored for ayear in darkness.

DOI:

10.1134/S000368380906012X

APPLIED BIOCHEMISTRY AND MICROBIOLOGY

Vol. 45

No. 6

2009

ANTIOXIDANT PROPERTIES OF ESSENTIAL OILS 643

dry leaves cinnamon (

Cinnamomum zeylanicum

Bl.),marjoram (

Origanum majorana

L.), laurel (

Laurusnobilis

L.), ginger (

Zingiber officinale

L.), garlic(

Allium sativum

L.), and clove bud (

Caryophyllus aro-maticus

L.) (company “Plant Lipids Ltd.”, India).To estimate the antioxidant properties of essential

oils and their mixture, 200 ml of n-hexane were solutedby 600

μ

l trans-2-hexenal (3

μ

l/ml) and 400

μ

l unde-cane (2

μ

l/ml), which was an internal standard. Thesolution was separated into 3-ml aliquots, which wereplaced in 5-ml glass vials and then 10

μ

l (3.33

μ

l/ml),50

μ

l (16.5

μ

l/ml) or 210

μ

l (70

μ

l/ml) of essential oilswere added. Oil was not added in the control sample.Each sample was prepared twice; the control samplewas prepared three times. Samples were stored in vialswith stoppers in light under room temperature for40 days. Every week vials were opened and blown with10 ml of air with a pipette. The quantitative content of2-hexenal and components of essential oils in vialswere determined by capillary gas chromatographyevery 10 days from the beginning of storage.

Gas-chromatography analysis of the essential oilssamples and control sample was conducted on a Kri-stall 2000M chromatograph (Russia) with a flame ion-ization detector and an SPB-1 silica capillary column(50 m

×

0.32 mm, phase layer 0.25

μ

m). The analysisof samples was conducted with the programming of thecolumn temperature from 60 to 250

°

C at a rate of8

°

C/min under the temperature of detector and injectorat 250

°

C. The rate of the carrier gas, helium, throughthe column was 1.5 ml/min. We analyzed 2

μ

l of hexanesolutions at once. The identification of components inoil samples was carried out on the basis of retentionindices by their comparison with the literature [26] orexperimental data obtained by us. The quantitative con-tent of 2-hexenal and components of essential oils wascalculated by the ratio of peak areas, which corre-sponded to the substances and internal standard. Theextent of oxidation of 2-hexenal and essential oils com-ponents (%) was determined in reference to their con-tent in initial samples.

RESULTS AND DISCUSSION

The oils that we chose contained many commoncomponents but differed in their quantitative and qual-itative composition. We used capillary gas chromatog-raphy, which is why we could estimate changes in thecontent of each oil component in two to three modelsystems with different oil concentrations and in pureoil, as well as distinguish the oxidation products of themain components. Furthermore, due to the comparisonof oil composition and the oxidation rates of compo-nents, we managed to reveal some regularity, whichenables us to predict and regulate oil composition toobtain stable mixtures. This is very important becauseessential oils are currently widely used in industry andmedicine. Usually the recommended storage time foroils is 1 year; however, nobody has studied yet what

really happens to oils during this period. Earlier westudied the changes in the composition of coriander,laurel, marjoram, and fennel oils during storage of pureoil amples away from light and in light but in bottles ofdark glass [27–29]. It was established that the main pro-cess is oxidation of the oil components. Thus, wefound, and then it was proved in [10, 11], that cyclicmonoterpene hydrocarbons

α

-

and

γ

-terpinenes arecompletely oxidized into aromatic hydrocarbon p-cymene. We also found oxidation products of othercomponents of essential oils—oxides, alcohols, andaldehydes [26–29].

To estimate the antioxidant properties of essentialoils, we used a model system of 2-hexenal daylight-induced autooxidation, which has been widely used insimilar studies [7, 8, 20–25]. As a criterion for the esti-mation of antioxidant properties of essential oils, weused a quantity of 2-hexenal, which remained unoxi-dized after 40 days in regards to the initial quantity (%).Figure 1 presents the results of relative AOA values ofthe 14 essential oils studied. The model systemincluded garlic, cinnamon leaves, marjoram, clove bud,nutmeg, laurel, or white pepper in two concentrations:3.3

μ

l/ml and 16.5

μ

l/ml. The quantity of 2-hexenal was3

μ

l/ml. For the essential oils of ginger, juniper berry,fennel, black pepper, caraway, and cardamom, we stud-ied an additional third system in which the content ofoil was 70

μ

l/ml of hexane solution. As is clearly seenfrom Fig. 1, there was a dependence between concen-tration and activity for all oils with the exception of gar-lic and clove bud oils. It is noteworthy that the increasein activity was usually not in proportion to the growthof essential oil concentration. The systems with mini-

100

80

60

40

20

0

AOA, %

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Control C1 C2 C3

Fig. 1.

Relative antioxidant activity of essential oils;(

1

) control (2-hexenale), (

2

) garlic, (

3

) clove bud, (

4

) cinna-mon leaves, (

5

) ginger, (

6

) nutmeg, (7) mace, (

8

) laurel,(

9

) marjoram, (

10

) caraway, (11) fennel, (

12

) juniper berry,(

13

) black pepper, (

14

) white pepper, and (

15

) cardamom.Concentration of essential oils (

μ

l/ml): C1,3.3; C2, 16.5;and C3, 70.

644


Vol. 45

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2009

MISHARINA

et al.

mal content of cinnamon leaves, ginger, laurel, mace,and nutmeg oils (3.3

μ

l/ml) had AOA more than 50%.The increase in the content of these oils by five timeswas accompanied by an increase in AOA by 20–30%,and the further increase in content of ginger and maceoils by four times (from 16.5 to 70

μ

l/ml) led to thegrowth of oil activity by only 5–7%. The diluted solu-tions (3.3

μ

l/ml) of juniper berry, black and white pep-per, fennel, caraway, and cardamom oils had very lowAOA: 20–28%. The increase in concentration of suchoils by five times (from 3.3 to 16.5

μ

l/ml) led to anincrease in AOA by 2.5–3 times. The further increase inconcentration of essential oils up to 70

μ

l/ml either didnot change AOA, as for juiper berry and black pepperoils, or it led to an increase by 7–10%. The stableincrease in AOA from 21 to 45% and 66% with anincrease in oil concentration by five and four times wasrevealed only for cardamom oil (Fig. 1).

The essential oil of garlic possesses the highestAOA (90%) and this activity depended poorly on oilconcentration (Fig. 1). This oil was a mixture ofpolysulfides with methyl and allyl substituents. Toassess changes in the content of the main oil compo-nents in the process of oxidation or storage, we calcu-lated the ratio of quantity of each component of the oxi-dizing system to its initial quantity, which was regardedas 100%. This allowed us to assess the extent of oxida-tion of the component or the increase in its content incase this component was the final oxidation product ofother essential oil components. Figure 2 presents

changes in content of the main polysulfides during thestorage of the hexane solution of the essential oil of gar-lic for 2 months. As can be seen, during this time thequantity of polysulfides increased, while that of three-and tetrasulfides decreased; that is, it happened dispro-portionally. In the case of the longer storage period ofpure oil, such changes were noticed after 6 monthsaway from light and 4 months in light. Also, except fordisproportionality, we revealed polysulfide oxidationwith the formation of sulfoxides and sulfonic acids. Asa result, such oil was of no use.

The inhibition of 2-hexenal oxidation by clove budoil was also hardly depended on the concentration andwas 75–78%. The essential oil of cinnamon leaves pre-served 2-hexenal at 66–78% (Fig. 1), while the concen-tration increased by five times. This oil differed fromclove bud oil by its more complex composition. It con-tained approximately 10% of monoterpene hydrocar-bons and alcohols, cinnamaldehyde, and cinnamyl ace-tate. The content of the main component eugenol wasless by 5% and the content of eugenyl acetate was moreby 7% than in clove bud oil. AOA and composition sta-bility of both oils were high. In hexane solution, bothoils did not change their composition for 60 days. Pureindividual oils may also be stable when stored awayfrom light for 2 years and in light for 8 months. In bothoils, we did not notice oxidation even of terpene hydro-carbons.

The AOA of the essential oils of nutmeg and maceincreased from 53 to 69% and from 63 to 78% accord-ingly, with an increase in their concentration in modelsolutions (Fig. 1). These oils were close in the quantita-tive and qualitative content of components. The maincompounds in oils were monoterpene hydrocarbonsand alcohol 4-terpineol. The aroma of this spice is dueto phenol derivatives—safrol, myristicin, and elemi-cin—the content of which in oil was from 0.9 to 2.6%.These compounds together with terpene hydrocarbonscorresponded to the AOA of oils. During the autooxida-tion of oils in hexane solutions for 40 days, only thecontent of

α

-

and

γ

-terpinenes decreased by three tofour times and the content of their oxidation product, p-cymene, increased. In the process of storage of theseoils in pure form for 4 months, their content did notchange, but storage for 1 year led to the almost com-plete oxidation of

α

-

and

γ

-terpinenes and the oxidationof 50% of caryophyllene with the formation of caryo-phyllene oxide.

The AOA of the essential oil of ginger was studiedfor three model systems with oil concentrations of 3.3,16.5, and 70

μ

l/ml. In the first system, oil inhibited theoxidation of 2-hexenal by 54%; in the second, by 78%;and in the third, by 94% (Fig. 1). This is very high activ-ity taking into consideration the fact that oil does notcontain phenol derivatives. It consisted of sesquiter-pene hydrocarbons, which differed in stability. Thedynamics of changes in the main components of theessential oil of ginger for the system with an oil concen-

120

110

100

90

80

70

600 30 60

%

days

1

2

3

4

5

Fig. 2.

Content of polysilfides (% from initial) in essentialoils of garlic in the oxidation process in hexane solution:(

1

) diallyldisulfide, (

2

) methylallyldisulfide, (

3

) diallyl-trisulfide, (

4

) methylallyltrisulfide, and (

5

) diallyltetrasul-fide.


Vol. 45

No. 6

2009


tration 16.5

μ

l/ml is presented in Fig. 3. The main oilcomponent—zingiberene—oxidizes faster than all oth-ers. After 60 days of storage, its content in the first solu-tion decreased by 20 times, in the second it decreasedby seven times, and in the third it decreased by2.5 times. Also, the content of bisabolenes and ses-quiphellandrene decreased (Fig. 3). It is interestingthat, in parallel to the decrease in zingiberene concen-tration, we saw an increase in α-curcumene content.The structure of zingiberene is similar to the structureof α-terpinene. Both compounds have a similar hexam-erous cycle with two double bonds. The oxidation prod-uct of α-terpinene was p-cymen [27–29]. Probably, zin-giberene oxidized in α-curcumen, which is an aromaticcompound similar to p-cymen. The content of zingib-erene in ginger oil is approximately 35%, and thus thisoil has high AOA. During storage of the essential oil ofginger away from light for 12 months, the content ofzingiberene decreased by two times and the content ofα-curcumen increased by 1.5 times. Such a change inthe oil composition significantly worsens its organolep-tic characteristics and physicochemical and biologicalproperties. This should be taken into considerationwhen using stored essential oil of ginger.

The essential oil of sweet marjoram contained from15 to 25% linalool, 4-terpineol, and γ-terpinene and didnot contain phenol derivatives. With the increase in oilconcentration, its AOA increased by 1.5 times and con-stituted 72% (Fig. 1). Figure 4 presents the quantity ofcompounds left after 40 days of oxidation (in percent-age from the initial quantity). During the storage of thediluted solution of oil, mono- and sesquiterpene hydro-carbons and even 4-terpeneol were significantly oxi-dized; in a more concentrated solution, only the con-tentof α- and γ-terpenenes decreased significantly.The content of oxidation products of these com-

pounds, p-cymene, increased. In both solutions thecontent of geraniol changed slightly. The individualmarjoram oil preserved content stability away fromlight for a year; in light, noticeable oxidation beganafter 4 months of storage [28].

Black and white pepper and juniper berry oils dem-onstrated a significant influence of the concentration onantioxidant properties. They had practically the samequantitative composition of components—mono- anddisesquiterpene hydrocarbons. In hexane solution theydid not show antioxidant properties because the oxida-tion of 2-hexenal happened to the same extent as in thecontrol sample, which did not contain essential oils. Ina concentration 16.5 μl/ml, the essential oil of blackpepper hindered the oxidation of 2-hexenal by 58%, theessential oil of white pepper hindered it by 49%, andjuniper berry oil hindered it by 65%. In a solution witha concentration of 70 μl/ml, the essential oil of blackpepper had an AOA of 62% and that of juniper berry,66% (Fig. 1). In diluted solutions, during 40 days,nearly all components of the essential oil were oxi-dized. Figure 5 shows the changes in the content of themain oil components for a solution with a concentrationof 16.5 μl/ml. As is seen, after 40 days the content of α-and γ-terpinenes in oils decreased by five to six timesand that of β-cariophyllene, by 2.5–3 times; the contentof other components changed insignificantly. We haveshown that the oxidation of caryophyllene began whenthe majority of α- and γ-terpinenes were oxidized. Dur-ing storage of individual oils away from light, a similarprocess was detected after 8 months. By that time, the

120

100

80

60

400 20 40 60 days

%

1

2

3

4

5

100

80

60

40

20

01 2 3 4 5 6 7 8

I II

%

Fig. 3. Content of main components (% from initial) ofessential oil of ginger in the oxidation process in hexanesolution: (1) α-curcumene, (2) zingiberene, (3) α-bisab-olene, (4) β-bisabolene, and (5) sesquiphellandrene.

Fig. 4. Influence of concentration of marjoram oil (I—3.3 μl/ml, II—16.5 μl/ml) on the degree of oxidation of itscomponents (% of initial): (1) sabinene, (2) myrcene, (3) α-terpinene, (4) γ-terpinene, (5) α-terpinolene, (6) β-caryo-phyllene, (7) geraniol, and (8) 4-terpineol.

646

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MISHARINA et al.

content of terpinenes was 2–10% of the initial contentand that of caryophyllene was 80–85%, whereas thecontent of caryophyllene oxide increased by 2–2.5 times and that of p-cymene increased by four times.Thus, the content of γ-terpinene and caryophylleneoxide may be an indicator of the freshness and qualityof the essential oils of black and white pepper. Addi-tional experiments showed that the stability of theseoils is much higher than in the mixture of, for example,black pepper, juniper berry, garlic, or nutmeg.

With the increase in fennel and caraway essentialoils concentration in hexane solution, their AOA alsoincreased by 2.7–3 times and was 60% for fennel and56% for caraway. In a solution with an oil concentrationof 70 μl/ml, AOA was 71 and 67%, respectively (Fig. 1).In a diluted solution of fennel oil, trans-anetol oxidizedcompletely after 40 days to an anise aldehyde; with anincrease in concentration, the degree of oxidationdecreased and constituted 50% at a concentration of16.5 μl/ml and 46% at a concentration 70 μl/ml. A sim-ilar oxidation of anetol to anise aldehyde was discov-ered in a study of the stability of fennel oil in light andaway from light [29]. In caraway oil, limonene wasunstable. In a diluted solution after 40 days, only 6% ofit was left; of carvon only 51% was left; in more con-centrated solutions, limonene remained at 78–82% andcarvon remained at 94–95%. We showed that in themixture of fennel, laurel, and coriander oils, the oxida-tion of the oil components, including limonene andanetol, did not happen and this mixture remained stablefor 12 months [29].

The essential oils of laurel and cardamom had closecompositions of the main components; the difference in

aromas was due to the presence in cardamom oil of 1%of neryl and linalyl acetates and nerolidol. Both oilscontain sabinene and 1,8-cineol, but the essential oil oflaurel in hexane solution hindered the oxidation of2-hexenal 1.5 times more effectively than the essentialoil of cardamom (Fig. 1). After 40 days of autooxida-tion in light in hexane solution, laurel oil remained sta-ble. Earlier we had established that individual pure lau-rel oil did not change its content in storage away fromlight for 2 years [29]. The stability of the essential oil ofcardamom, as well as its AOA, depended on its concen-tration in hexane solution. So, at a concentration of3.3 μl/ml, The quantity of sabinene decreased by fivetimes and terpinyl acetate decreased by two times, α-and γ-terpinenes oxidized completely. In more concen-trated solutions, only α- and γ-terpinenes oxidizedcompletely; the content of other components in solu-tions with oil concentrations 16.5 and 70 μl/ml changedin the same way. It is noteworthy that the AOA of car-damom oil increased with increasing concentration inthe model system (Fig. 1). Probably, they were mainlyα- and γ-terpinenes, which corresponded to the AOAproperties of this oil. During storage of the essential oilof cardamom, after 100 days we noticed significant oxi-dation of α- and γ-terpinenes; the quantity of sabinenedecreased by 65% and that of terpinyl acetate decreasedby 35% (Fig. 6). The reason for changes in the behaviorof essential oils of laurel and cardamom was probablythat laurel oil contained approximately 2% of methyleugenol, which possesses strong antioxidation proper-ties. Due to its presence, the laurel oil has higher AOAand was resistant to oxidation. Addition to the carda-mom essential oil at least 0.5% of clove bud oil, which

100

80

60

40

20

0

%

1 2 3 4 5 6 7

I II III100

90

80

70

60

50

40

300 20 40 60 100

days

%

1

2

3

4

Fig. 5. Content of main components (% of initial) in(I) black pepper, (II) white pepper, and (III) juniper berry inthe oxidation process in hexane solution: (1) α- andβ-pinenes, (2) sabinene, (3) myrcene, (4) 3-carene, (5) islimonene, (6) α- and γ-terpinenes, and (7) β-caryophyllene.

Fig. 6. Content of sabinene and terpinyl acetate (% of ini-tial) in cardamom oil and its mixture with 0.5% clove budoil during storage: (1) and (2) sabinene and terpinyl acetatein cardamom oil, and (3) and (4) sabinene and terpinyl ace-tate in a mixture of cardamom oil and 0.5% clove bud oil.

APPLIED BIOCHEMISTRY AND MICROBIOLOGY Vol. 45 No. 6 2009


contained approximately 80% eugenol, significantlyincreased the resistance of all components to oxidationin comparison with individual cardamom oil (Fig. 6).

Thus, our research and the literature data show thatessential oils are effective natural antioxidants, whichare able to compete with synthetic ones. The antioxi-dant properties of essential oils are determined by theircomposition. Oils with high contents of substitutedphenols are able to significantly hinder the oxidationprocesses of labile unsaturated aldehydes even in lowconcentrations. The antioxidant properties of essentialoils consisting of terpene hydrocarbons and alcoholsare determined by α- and γ-terpinenes and their sesquit-erpene analogs. We revealed a significant influence ofthe concentration of such oils on their antioxidant prop-erties. It was established that in the oxidation of themain components of essential oils, substances areformed that are present in natural essential oils. The sta-bility of the composition of essential oils increased withan increase in their concentrations in model solutions.The oxidation of substances in pure essential oils hap-pened slower than in solutions.

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