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Grasas y AceitesVol. 50. Fase. 5 (1999), 355-358 355

Antioxidan t activity of rosemary {Rosmarinus officinaiis L.) extracts on natural oliveand sesame oilsBy Musa zcan

Department of Food Engineering, Faculty of Agriculture, Selcuk University, 42031 Kenya, Turkey.R E S U M E N

Actividad antioxidante de extractos d e romero (Rosmarinusofficinalis L) en acei tes de ssamo y de ol iva.Se determinaron las actividades antioxidantes de extractos de c loroformo y de metanol de romero (Rosmarinus officinalis L.) en aceites de ssamo y de oliva almacenados a 55 C mediante medidasde los ndices de perxidos a intervalos regulares. Se uti l izaronconcentraciones al 1 % y 2% de extractos y cido ctrico. Los extractos (excepto para los das 1 2,1 6 y 20 de almacenamiento deaceite de oliva) m ostraron una alta actividad antioxidante comparados con la muestra control en am bos ace ites. Los efectos antioxidantes de ambos extractos y los niveles de cido ctrico en elaceite de oliva tuvieron diferencias signif icativas despus de 4das de almacenamiento (p < 0.01). La concentracin ms efectiva en aceite de ssamo durante el almacenamiento fue del 2%en extracto de cloroformo. Adem s, especialmente concentraciones del 2% de am bos extractos de disolventes de romero mostraron una actividad antioxidante significativa en comparacin con elcido ctrico en aceite de ssamo .PALABRAS-CLAVE:Aceite de oliva - Aceite de ssamo - Efecto antioxidante - Estabilidad - R omero.

SUVIIVIARYAntioxidant activity of rosemary {Rosmarinus officinalisL.) extracts on natural ol ive and sesame oi ls.The antioxidant activities of chloroform and methanol extracts ofrosemary [Rosmarinus officinalis L.) were tested in natural olive andsesame oils stored at 55 C, by measuring peroxide values afterregular intervals. The con centrations of extracts and citric acid hadbeen used as 1 % and 2% . The extracts (except for 12,16 and 20

days in storage of olive oi l) exhibited high antioxidant activitycompared with control sample in olive and sesame oil. Antioxidanteffects of both extracts and citric acid levels in olive oi l showedstatistically different after from 4 days of storage (p < 0.01 ). The mostef fect ive concentrat ion on sesame oi l during storage had 2%chloroform extract. Furthermore, especially 2 % concentrations ofboth solvent extracts o f rosem ary show n significantly antioxidativeactivity in compared w ith citric acid on s esame o il.KEY-WORDS: Antioxidant effect - O live oil - Rosemary - Sesame oil - Stability.

1 . INTRODUCTIONSynthetic antioxidants are widely used to retardundesirable changes as a result of oxidation in many

foods. Excessively oxidized fats and oils are notsuitable for nutritive purposes. Because, theoxidation products of oils have toxic effects. Manysynthetic substances such as butylated hydroxyanisol(BHA), propyl gllate and citric acid are comnnonlyused in lipids to prevent oxidation. Recently, thesesynthetic substances have been shown to causesuch as enlarge the liver size and increasemicrosom al enzym e activity. Therefore, there is needfor other compounds to effect as antioxidants and torender food products safer for mankind (Farag eta/.,1989, Farag eia/.,1990, Brookman, 1991).Plant originated antioxidants have been used inoils or lipid containing foods in order to preventoxidative deterioration (Gur and Gulden, 1997). Theantioxidant activity displayed by spices or otherantioxidants depends on several factors such as theconcentration, the temperature, the hydrophobic,hydrophylic or amphiphatic character, the presenceof synergists and the chemical nature of the food ormedium to which they are added (Logouri andBoskou, 1995). Chang et al. (1977) obtained similarresults while investigating the antioxidative effect ofrosemary and sage due to the peroxide value.Essential oils such as rosemary and sage oils lackany antioxidant activity although the herbs areknown antioxidants and find many applications infood preparations (Chipault et a!., 1952; C hipault eta!., 1956; Bishou eta!., 1977; Hermann eta!., 1981;Barbut efa/., 1985; Pizzocaro eta!., 1985; Inatani etal., 1984; Houlihan et al., 1984; zcan and Akgl,1995). Naturally occurring compounds in rosemaryextracts (Wu etal., 1982; Ho etal., 1983) have beenreported to exhibit antioxidant properties greaterthan BHA and equal BH T

The extracts rosemary (Chang et al., 1977;Economou et al., 1991 ; Banlas et al., 1992), wereexamined in order to determine their antioxidativeactivity against autoxidation in different substrates,mostly in lard. Their antioxidative activity depends onthe solvent used, but the structure activityrelationship of them have not been completelyinvestigated (Chang et al., 1977; Economou et al.,1991; Banlas e a/., 1992).Antioxidant effects of 35 methanol extracts and 20essential oils from Turkish spices were tested in sunfloweroil stored at 70 C (zcan and Akgl, 1995).

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356 Grasas y Aceites

Thus, the objective of this study was to evaluateto efficacy of adding a natural rosemary oleoresin tosesame and olive oils and to compare it with acomm ercial citric acid used as an a ntioxidant.

2. MATERIALS AND METHODSPlant Material and Preparation of Extracts:Rosemary was purchased from market. Groundmaterial was extracted with pure methanol andchloroform for 3 hr in a stirred vessel, at a liquid-to-solidratio 4:1 and a temperature of 60 C. The m ixture wasfiltered and concentrated in rotary evaporator andsolvent was completely remove d. Extracts were kept insealed bottles under refrigerated using.Olive and Sesame Oils: Naturel olive and sesam eoils without adding any antioxidant were kindly suppliedby Kristal and Salur company in Yzmir and Kenya,respectively. Their peroxide numbers w ere 15 and 18.1meq/kg, the same respectively. The sesame oil wasselected for their high degree unsaturation levels andfor being the most widely used as edible and tehina(sesame paste) oil in Turkey.Citric Acid: Citric acid (E.M erck, Darmstadt) waspreferred because of using commonly as prevent tothe deterioration at oil company.Antioxidant Activity Measurement: The rate ofoxidation was followed by periodic determination ofperoxide values of the oil stored at 55 C by usingchloroform and methanol as extraction solventswhich are at different polarities. A calculated quantityof the extract and citric acid wa s added at the 1 an d2% concetrations into olive and sesame oil, and themixture was stirred. A control sample was preparedunder the same conditions without adding anyantioxidant. All samples of 20 g each were storagedin 10 X 100 mm open beakers at 55 C in the dark.For the peroxide number, a known weight of oliveand sesame oils (2 g) was dissolved in a mixture ofCH3COOH: CHCI3 (3:2, v/v), and saturated solutionof Kl (1ml) was then added. The liberated iodine wastitrated with sodium thiosulfate so lution (0.01 N) in thepresence of starch as an indicator (A.O.C.S., 1989).The codes of the samples are shown in Table I. Itshould be mentioned that in experiments, with theplant extracts at various concentrations, raw oliveand sesame oils were used.Statistical Analyses: Findings of*the researchwere analysed for s tatistical significance by analysesof variance, and differences among groups were

established according to Dzgnes et al. (1987).Experiments and analysis were replicated andduplicated.

Table IThe codes of the extract and citric acidadded samplesOlive oil samples

S^a me di samples

ControlContaining 1% (w/w) chloroform extract of rosemary"

Control

21212

Methanol

citric acid

Containing 1 % (w/w) chloroform extract of rosemary

- 21212

Methanol

citric acid

AoA iA2A3A4AsAsBoBiB2BsB4BsBe

3. RESULTS AND DISCUSSIONTable II represents the antioxidant effect of thechloroform and methanol extracts of rosemary, andcitric acid in olive and sesame oils as determined bythe peroxide value.After 4 days, the extract concentrations showedantioxidant effect in varying degrees on olive andsesame oil compaered with the control test (p < 0.01).Peroxide values of all the samples partly increasedduring storage. After 12 days, peroxide values ofsesame oil at all the concentrations had higher thanthose of olive oil. At both extract concentrations ofchloroform and methanol peroxide values were highaccording to control on 16 and 20 days. But,antioxidant effects of both solvent extractconcen trations (1% ) in olive oil are higher than thatof the same citric acid concentration as from 4,8 and12 days. But, the same concentrations (1% ) ofextracts in sesame oil showed antioxidant effectaccording to citric acid (1% ) concentration.The 2% concentration of chloroform andmethanol in sesame oil had more effect than those ofonly 2% concentration of chloroform and methanolextracts and both concentrations of citric acid (p < 0.01 ).The most effective concentration on sesame oilduring storage had 2 % chloroform (Fig.1). Furthermore,especially 2% levels of both solvent extracts ofrosemary exhibited remarkable antioxidative activity incomparison w ith citric acid on sesame oil (p < 0.01).Overall strongest activity of rosemary was notsurprising, because of various findings reported onits stabilizing effect (Ch ang etal., 1977; Braceo et al.,1981), and related active components such as

carnosol, rosmanol, rosmariquinone, carnosic andursolic acids etc. (Wu et al., 1982; Inatani et al.,1983; Houlihan tal., 1985; Chen tal., 1992).

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V ol .5 0 . F as e. 5 ( 1 9 9 9 ) 357

Table IIAntioxidant effect of rosemary extract added to olive and sesam e oils* stored in thie darl< at 55 C (meq/kg)Days

4

8

12

16

20

24

Oils

OliveSesame

OliveSesame

OliveSesame

OliveSesame

OliveSesame

OliveSesame

Control

25.00 0.62K**51.70 0.32F28.20 0.52J72.10 0.65E31.70 0.70198.00 0.39D32.80 0.68H104.9Q 0.65C33.50 0.74H106.60 0.39B48.90 0.79G151.20 0.99A

Chloroform Extract (%)1

23.70 0.63J49.70 0.87F30.20 0.76156.70 0.59E34.10 0.54H65.80 0.29D34.50 0.63H68.80 0.76035.60 0.78H76.80 0.85B39.50 1.87G82.12 1.42A

219.30 0.64H23.00 1.15G20.70 1.41 H24.30 0.59G32.40 0.42F34.50 1.20E34.30 0.39E48.50 0.84C35.00 0.32E51.90 1.28B38.80 0.65D55.62 0.39A

Methanol Extract (%)1

24.30 0.29H21.20 0.18125.60 0.55G

24.90 1.45GH33.50 0.66F44.20 0.39D33.90 0.57F49.00 0.38C34.30 0.41 F52.90 0.47B37.90 0.33E65.80 0.82A

224.50 0.32126.80 0.39H30.50 1.77G38.30 0.97E31.30 0.84G45.60 0.59D31.40 0.80G49.50 0.65C34.90 1.34F54.80 0.41 B38.00 1.28E66.40 0.42A

Citric Acid (%)1

19.50 1.1 OJ49.00 0.29E25.05 0.73156.00 0.18D27.10 0.42H

57.80 0.55CD36.20 1.50G58.70 0.79C37.00 0.94G61.10 1.05B40.80 0.74F159.70 2.26A

219.40 0.92137.60 0.67E29.80 0.65H53.90 0.91 D

31.00 1.13GH77.80 0.1OC32.50 1.14G

79.20 + 0.70BC35.60 + 1.16F79.70 0.46B

36.22 0.47EF161.50 0.71 A

Initial peroxide valu e of the olive and sesame oil were 15.0 and 18.1 meq/kg, respectively.* Differences among means indicated with majuscules are significant in p< 0.01.

Figure 1Changes inperoxide values insesame oil that rosemaryextract and citric acid

4. CONCLUSIONSThe results indicated that rosemary extract

obtained by different polarities solvents anantioxidant activity on olive and sesame oils at 55 C.Antioxidant effects of both extracts and citric acidlevels in olive oil had found significantly different afterfronn 4 days of storage. However, antioxidant effectsof both extract concentrations of solvents weresilightly weaker than that of control on 16 and 20

days of storage. Peroxide values of sesame oil,especially 12 days, had higher than those of olive oilas from 12 days of storage. The reason for this isprobably that initial peroxide value of sesame oil washigher than that of other oil. However, it was seenthat the antioxidant activity of the extract depends onthe polarity of the solvents used for extraction.

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Recibido: Junio 1998Aceptado: Enero 1999

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