219-Article Text in Microsoft Word or LibreOffice File (Needed) - 219-1!10!20071008
219-Article Text in Microsoft Word or LibreOffice File (Needed) - 219-1!10!20071008
National Research Centre, Fats and Oils Dept., Dokki, Cairo, Egypt
RESUMEN 1. INTRODUCTION
Cambios producidos en la composición de aceites ve- Microwave energy, with its unique heating ability,
getales debido al calentamiento en microondas. offers many advantages for both home and industrial
food applications such as baking, cooking, thawing,
Se estudia el efecto del calentamiento en horno de microon-
das sobre aceites de diferente composición en ácidos grasos.
blanching, dehydration, pasteurization, sterilization
Aceites de girasol, soja, cacahuete y una mezcla de soja y caca- and tempering, also effects of microwave on food
huete al 50%, se calentaron durante 2, 4, 6, 8 10, 12, 15 y 18 mi- constituents as well as the formation of flavors and
nutos. Los valores de índice de peróxidos, acidez libre y colors in food have been studied (Decareau,1985;
absorbancia a 420 nm fueron proporcionales al tiempo de calen-
tamiento. Otras determinaciones incluyeron el contenido total en Riley, 1985; Rosenberg and Bogl, 1987; IFT, 1989;
tocoferoles mediante cromatografía en capa fina, la composición Giese, 1992). Microwave ovens are credited with
en ácidos grasos y en epoxiácidos mediante cromatografía gas lí- rapid heating rates and high efficiency, especially
quido, y la formación de dienos y trienos conjugados mediante es- because of their high penetration power (Riley, 1985;
pectrofotometría UV. Los resultados indicaron que el contenido en
tocoferoles disminuyó con el tiempo de calentamiento dependien- IFT, 1989; Burfoot et al., 1990). Numerous
do del tipo de tocoferol predominante y que los cambios estaban investigations have been done to study the effects of
relacionados con los encontrados para el índice de peróxidos. Los microwave on food constituents and various
ácidos poliinsaturados también decrecieron con el tiempo de ca-
lentamiento. Finalmente, los resultados obtenidos con la mezcla
chemical reactions are induced by microwave energy
de aceites de soja y cacahuete fueron muy útiles para interpretar (Finot, 1995). Lipid components of animal fats and
los resultados obtenidos con los aceites individuales. vegetable oils microwave heated were also
investigated (Yoshida el al., 1990; Yoshida et al.,
PALABRAS-CLAVE: Aceite vegetal -- Calentamiento -- Cam- 1992; Farag, 1994). It was found that the rate of
bios químicos -- Microondas.
quality deterioration, such as oxidation, depends on
the polyunsaturated fatty acid content (Yoshida et al.,
SUMMARY 1990; Lin et al., 1999).
In vegetable oils exposed to microwave energy,
Changes occurring in vegetable oils composition due the higher the amount of polyunsaturated fatty acids
to microwave heating.
in the oils, the greater was the rate of quality
The effect of microwave heating on three vegetable oils deterioration of the oils. The levels of free fatty acids
having different lipid compositions was studied. Sunflower, also increased in vegetable oil heated in microwave
soybean and peanut oils in comparison with oil admixture of oven (Yoshida et al., 1992).Thus, the changes in
soybean and peanut oil (1:1, w/w), were selected for this study. olive oil composition due to microwave heating were
Each oil was heated for 2, 4, 6, 8, 10, 12, 15 and 18 minutes in
microwave oven. Peroxide value, free acidity and colour studied by Cossignani et al. (Cossignani et al.,
absorbance (at 420 nm) were proportionally increasing with the 1998).The traditional parameters, including free
increase of heating period. Colour absorption threw light on the acidity, peroxide value and ultraviolet absorbance
formation of browning products arising from phospholipids during
microwave heating. Total tocopherol contents were determined by
values, were determined.
preparative thin layer chromatography, whereas the fatty acid Since tocopherols are very important biological
compositions and formed epoxy acid were analyzed by capillary and nutritive food components, the effect of
gas liquid chromatography. The formed conjugated dienes and microwave heating on the soybean tocopherols was
trienes were determined by UV spectrophotometry. It was found
that the total tocopherols of the microwave heated oils, decreased studied by Yoshida and Kajimoto (Yoshida and
depending on the type of the predominating tocopherols. Also a Kajimoto, 1989). They showed that the effects of
relation of peroxide formation, during microwave heating, with microwave treatment on the total tocopherols
changes in total tocopherol composition was discussed. It was content of soybean oil gradually decreased by
found that polyunsaturated fatty acids generally decreased by
increasing the heating period. The results obtained from the heating time.
heated oil admixture helped interpret the results obtained from In the present work, the objective was to study the
other heated individual oils. influence of microwave heating on the three selected
oils, i.e., sunflower, soybean and peanut oils, having
different fatty acid and tocopherol compositions. In
KEY-WORDS: Chemical changes -- Heating -- Microwave addition to these oils, a binary oil admixture from
-- Vegetable oil.
344 Grasas y Aceites
peanut and soybean oils (1:1 w/w) was prepared as 2.2.4. Color Index (CI)
a model to help interpret some results concerning
the microwave heating of different oils having As an index of colour development during MW
different contents of polyunsaturase and heating the spectrophotometric absorbance at 420
tocopherols. nm of a 2.5% w/v solution of oil in isooctane was
determined using a Shimadzu Spectrophotometer
2. MATERIALS AND METHODS (Yoshida and Kajimoto,1989).
Three oil seeds, namely, sunflower, soybean and (By preparative thin layer chromatography)
peanut (Season, 2000) were purchased from
Oilseed Crop Department, Ministry of Agriculture, Owing to the difficulties usually encountered in
Giza. isolating all individual tocopherols for their GLC
analysis (Dirks, 1965; Slover et al., 1967), it was
2.2. Methods advisable to determine total tocopherols
quantitatively by preparative thin layer
chromatography (PTLC). Thus, a sample of methyl
2.2.1. Lipid Extraction ester of each oil (previously transesterified (Barford
et al., 1963) was accurately weighed and applied as
Representative oilseed samples of sunflower, streaks on silica gel plates (300µ thickness of silica gel
soybean and peanut (500g of each) were ground and 60 GF254 nm, E.Merk). Standard tocopherol mixture
soaked in chloroform-methanol (2:1, v/v) with [alpha, gamma and delta tocopherols, supplied from
intermittent stirring to extract the oil. The extract of Nisshin Oil Mills (Japan)] was applied as reference
each sample was collected, filtered, dried over on one side of the plates. The plates were
anhydrous sodium sulphate and then evaporated developed with two successive solvent systems,
under reduced pressure at 50oC in a rotary 80/20/1 and 70/30/1 v/v/v hexane/diethyl ether/
evaporator and the samples were kept in stoppered glacial acetic acid. The tocopherols were detected on
dark glass vials in the refrigerator till analysis. In the chromatoplates as purple spots under ultra-violet
addition to the three extracted oils (sunflower, light. The different tocopherol zones (located with the
soybean and peanut), a binary oil admixture of help of the standard tocopherols) were scraped of
soybean and peanut, in an equal weight ratio, was the plates, extracted twice with moistened diethyl
prepared as a model . ether, dried over anhydrous sodium sulphate and
filtered. The ether was evaporated under reduced
2.2.2. Microwave Heating (MW) pressure and the residue was accurately weighed
using microanalytical balance (Mettler M5). The
A microwave oven (Samsung model 9245, results were the mean value of three determinations
MB245) having frequency of 2,450 MHz, was used and expressed as mg total tocopherols per 100g oil.
for heating the oil samples. Eight samples of each oil It is worthy to mention that standard tocopherols
(16 g each) were placed in eight petri-dishes (7 cm mixture was subjected to PTLC and the recovery
diameter). The samples of each oil were heated in was found to be more than 94%.
the MW oven for 2, 4, 6, 8, 10, 12, 15 and 18 minutes.
Temperatures in the oven reached 120o, 160o, 176o, 2.2.6. Fatty Acid Methyl Ester
197o, 210o, 216o, 222o and 227oC at the respective
heating periods. Each sample removed from the The oil samples were converted to their methyl
oven was kept immediately in a vacuum dissicator esters via transesterification using methanol
to cool it down to room temperature. The samples containing 0.04 N sodium methylate as a catalyst
were kept in dark glass vials in a refrigerator till (Barford et al., 1963). Hewelett Packard Model 6890
analysis. gas chromatograph was employed for the analysis of
fatty acid methyl esters under the following
2.2.3. Determination of Peroxide and Acid conditions: HP- INNOWax capillary column
Values (polyethylene glycol), 30.0 m x 530 µm, film thickness
1.0 µm; column temperature, 120-240oC at a rate of
Peroxide value and acid value were determined 10oC min-1; injection temperature, 250oC; split ratio,
according to Official American Oil Chemist’s Society 8:1; split flow, 120 ml min-1; gas saver, 20 ml min-1;
(AOCS) methods (AOCS, 1985). The values were and carrier gas, N2 with flow rate 15ml min-1; FID
expressed as meq of peroxide O2 / kg oil and mg detector temperature, 280oC; hydrogen flow rate, 30
KOH / g oil, respectively. ml min-1 and air flow rate, 300 ml min-1. Peak areas
Vol. 54. Fasc. 4 (2003) 345
16
were determined by electronic integrator and
percentage composition of fatty acids was 14
automatically calculated. Standard mixture of fatty
6
A sample of mixed fatty acid methyl esters of
soybean oil was subjected to partial epoxidation 4
using in-situ formed peracetic acid in the presence of
2
acid-cation exchanger (El-Mallah and El-Shami,
1975). The epoxy components were identified with 0
the help of standard GLC chromatogram (El-Mallah 0 2 4 6 8 10 12 14 16 18 20
et al., 1983) and thin layer chromatography-picration Exposu re time (min )
6
2.3. Expression of the Results
5
All the results are the mean values of more than
two experimental replications (n=2-4) for each 4
experimental analysis.
3
2
140
1,6
120
1,4 100
1,2
80
1
0,8 60
0,6
40
0,4
20
0,2
0 0
0 2 4 6 8 10 12 14 16 18 20 0 5 10 15 20
Exposure time (min)
Exposure time (min)
Sunflower Soybean Peanut Mixture Sunflower Soybean Peanut Mixture
Figure 4
Figure 3
Changes in the total tocopherol content of oils during
Effect of microwave treatment on oil colour index. microwave treatment at frequency of 2,450 MHz. Each value
Each value is an average of three to four determination and is is an average of three to four determination and is expressed
expressed in terms of absorbance at 420 nm. as mg /100g oil.
admixture > peanut oil > sunflower oil. This show that 15 and 18 min respectively. Table III shows the loss
the soybean oil colour is more affected by MW percentage in total tocopherol contents of the oil
heating than the other oils, whereas sunflower oil is samples and the oil admixture as a result of MW
less affected than any of the other oils. It is worthy to heating. It can be seen that peanut oil is highly
mention that, the darkening of oils during MW affected by MW heating since it exhibits highest
heating may be due to the presence of phospholipids percentage loss in tocopherol content during MW
in the oil that develop browning products having heating.
antioxidant activity (Dziedzic, 1984; Hudson and The interpretation of the changes in peroxide
Ghavami, 1984; Husain et al., 1986; Frankel, 1993). value can be attributed to the tocopherol type
Before discussing changes of tocopherols in MW predominating in the tocopherol composition. Since
heated oils it is worthy to mention that sunflower oil contains principally alpha-tocopherol,
alpha-tocopherols is the major tocopherol in exhibiting lowest antioxidation activity, the rate of
sunflower oil (Kanematsu et al., 1983; El-Shami et peroxide formation is markedly higher than those in
al., 1994) whereas gamma- and delta-tocopherols other oils. In contrast, soybean oil, containing high
are predominating in soybean oil (Kanematsu et al., antioxidation potency tocopherols (gamma- and
1983; Minar and Hassanein, 1991). However, in delta-tocopherols) resists efficiently the peroxide
peanut oil alpha- and gamma- tocopherols are the formation (Herb et al, 1964; Khafizov et al., 1975;
major tocopherol (Kanematsu et al., 1983). Ikeda and Fukuzumi, 1977; Yoshida and Kajimoto,
It was found feasible and simple to determine total 1989; Yoshida et al., 1992). It can be concluded that
tocopherol contents of the oils with the help of PTLC the gamma- and delta-tocopherols, as more powerful
and the results are represented graphically in Fig. 4. antioxidants than alpha-tocopherol, can protect oils
It was observed that, generally, there is a decrease in (Yoshida and Kajimoto, 1989 ). However, peroxide
total tocopherol content in all oil samples as MW formation in peanut oil (having the lowest content of
heating was proceeding. Thus in soybean oil the total tocopherols but nearly equal amounts of alpha- and
tocopherol content decreased from 120 mg/100g oil gamma-tocopherol) is slightly lower than that in
to 114, 100, 91, 80 and 75 mg/100g oil at 0, 2, 6, 10, sunflower oil. By admixing peanut oil with soybean oil
15 and 18 min heating respectively. While, the total in equal proportions, the stability is improved against
tocopherol content in sunflower oil decreased slightly oxidation during MW heating as indicated from the
from 70 mg/100g oil to 67, 66, 64, 63 and 58mg/100g peroxide curves in Fig.1 .These results,represented
oil, whereas, the total tocopherol contents in peanut graphically, confirmed those obtained from soybean
oil decreased from 25mg/100g oil to 22, 19, 16, 13 and peanut oils. Thus, the peroxide formation curve
and 8 mg/100g oil. On the other side, the total of the oil admixture is an intermediate between
tocopherol content in oil admixture decreased from soybean and peanut oil curves.
75 mg/100g oil to 71, 67, 63, 55 and 50 mg/100g oil Fatty acid composition at selected heating periods
during the selected MW heating periods 0, 2, 6, 10, was determined to follow any significant changes in
Vol. 54. Fasc. 4 (2003) 347
Table I
Fatty acid composition of oil samples subjected to microwave heating determined by gas liquid
chromatography
Sunflower oil Soybean oil Peanut oil Oil admixture (soybean : peanut
Oils subjected to MWH*
oil, 1:1 w/w)
Heating Time (minutes) 0 6 10 18 0 6 10 18 0 6 10 18 0 6 10 18
Fatty acid composition(%)
Myristic 0.2 0.2 0.2 0.3 0.4 0.3 0.4 0.5 0.0 0.0 0.0 0.0 0.2 0.2 0.3 0.2
Palmitic 9.5 9.2 9.3 9.3 8.5 9.0 9.3 9.3 8.8 8.9 8.8 9.4 9.2 9.3 9.5 9.4
Stearic 0.1 0.1 0.0 0.0 3.6 3.5 3.6 3.9 2.9 2.9 2.8 2.9 3.2 3.3 3.0 3.4
Oleic 55.0 54.2 53.5 53.0 21.9 20.5 20.0 19.5 48.6 46.0 45.7 44.5 35.3 34.0 33.4 32.9
Linoleic 32.1 31.5 30.0 29.6 57.1 55.2 54.0 53.0 32.2 31.0 30.5 30.0 44.9 44.0 43.5 43.0
Linolenic 0.3 0.3 0.3 0.5 6.1 5.8 5.2 5.5 1.5 1.6 1.2 1.4 4.0 3.6 3.4 3.5
C20−C24 2.8 2.0 3.5 4.5 2.4 2.8 5.1 3.8 6.0 6.9 7.0 8.0 3.2 3.3 3.8 3.7
Others 0.0 2.3 2.9 2.6 0.0 2.4 2.2 4.4 0.0 2.4 3.6 3.6 0.0 2.1 2.9 3.8
Total oxygenated (epoxides) 0.0 0.2 0.3 0.2 0.0 0.5 0.2 0.1 0.0 0.3 0.4 0.2 0.0 0.2 0.2 0.1
Table II
UV Spectrophotometric determination of the formed conjugated dienes and trienes in oils subjected
to MW heating
Diene % (234 nm) in MW heated oils Triene % (268 nm) in MW heated oils
Heating time Sunflower Soybean Peanut Oil admixture (soybean : Sunflower Soybean Peanut Oil admixture (soybean :
(minute)
oil Oil oil peanut oil, 1:1 w/w) oil Oil oil peanut oil, 1:1 w/w)
0 0.0525 0.2150 0.3701 0.2512 0.0150 0.0042 0.0738 0.0411
6 0.5733 0.3956 0.5287 0.4040 0.0991 0.0583 0.0791 0.0507
10 0.9810 0.7509 0.7484 0.6241 0.0648 0.1565 0.0972 0.0950
18 1.0698 1.0483 0.8592 0.8720 0.1988 0.2013 0.1250 0.2132
* Each value represents an average of three to four determinations.
fatty acid profile and to detect the formation of any 1983; Megahed, 2001). From the results obtained,
unusual oxygenated compounds (Table I). It was found the following conclusions were derived out:
that oleic and linoleic acids generally decreased by 1. The tocopherols are unstable in the presence
prolonged heating. On the other hand it was also able to of unsaturated fats, particularly those rich in
identify two epoxy components as trace amounts that polyunsaturates and losses in tocopherols may be
stood for epoxy oleate and epoxy stearate as compared attributed mainly to degradation and partly to the
with the chromatograms of the prepared partially peroxidation of the unsaturated oils (Yoshida and
epoxidized soybean oil. It is worthy to mention that Kajimoto, 1989 ). Accordingly, oils containing the
these epoxy components were firstly identified by higher polyunsaturates content, cause losses in
chromatographic picration technique (El-Mallah and tocopherol content during MW heating (Nelis et al.,
El-Shami, 1975; El-Mallah et al., 1983). 1985; Yoshida and Kajimoto, 1989).
With respect to conjugated fatty acid formation 2. MW heating causes the formation of very
during MW heating, it was found that as MW heating lower amounts of some oxygenated compounds,
was progressing, the amount of conjugated dienes particularly epoxides that can be subjected to
and trienes gradually increased (Table II). It is worthy decomposition at prolonged MW heating.
to mention that the conjugated dienes were formed In addition, it was reported that the phospholipid
at, somewhat, higher levels than the conjugated constituents of the oils, even in lower concentrations,
trienes. The conjugation of polyunsaturates can be could act synergistically with tocopherols at higher
associated with the oxidation process during MW temperatures (Dziedzic, 1984; Hudson and
heating (Frankel, 1961; Herb et al., 1964; Hamilton, Ghavami, 1984; Husain el al., 1986; Frankel, 1993).
348 Grasas y Aceites
Table III
Percentage weight loss of total tocopherols of oil samples subjected to microwave heating
Heating time
Oil (minute) 2min 6min 10min 15min 18min
subjected to
MWH*
Sunflower oil 4.2 5.7 8.5 10.0 17.0
Megahed, G.M. (2001). Microwave Roasting of Peanuts: Stahl, E. (1966). Dunnschicht-Chromatographie, Springer
Effects on Oil Characteristics and Composition. Verlag, Berlin/Heideberg / New York.
Nahrung/Food, Accepted for publication. Yoshida, H. and Kajimoto, G. (1989). Effects of Microwave
Minar Mahmoud, M.Hassanein (1991). Changes in the Energy on the Tocopherols of Soybean Seeds. J. Food
Content and Composition of Lipids during Maturation Sci. 54, 1596-1600.
of Soybean and Sunflower Seeds. Submitted for the Yoshida, H.; Hirooka, BN. and Kajimoto, G. (1990).
Degree of M.Sc., University of Ain Shams, Faculty of Microwave Energy Effects on Quality of Some Seed
Science, Cairo, Egypt. Oils. J. Food Sci. 55, 1416-1421.
Nelis, H.J. ; De Bevere, V.O.R.C., and De Leenheer, A.P. Yoshida, H.; Kajimoto, G. and Emura, S. (1993). Antioxidant
(1985). Vitamin E ; Tocopherols and Tocotrienols In Effects of delta-Tocopherols at Different Concentration
Modern Chromatographic Analysis of the Vitamins. in Oil during Microwave Heating. J. Am. Oil. Chem. Soc.
Ch.3. A.P. De Leenheer, W.E. Lambert and M.G.M. de 70, 989-995.
Ruyter (Ed.), Marcel Dekker, NewYork, p. 129. Yoshida, H.; Kondo, I. and Kajimoto, G. (1992). Effects of
Rosenberg, U. and Bogl, W. (1987). Microwave Thawing, Microwave Energy on the Relative Stability of Vitamin
and Baking in the Food Industry. Food Technol. 41, E in Animal Fats. J. Sci Food Agric. 58, 531-534.
85-92. Yoshida, H.; Tatsumi, M. and Kajimoto, G. (1992). Influence
Ryley, 3. (1985). The Nutritional Effect of Microwave of Fatty Acids on the Tocopherol Stability in Vegetable
Heating. BNF Nutr. Bull. 14, 46-62. Oils During Microwave Heating. J. Am. Oil Chem. Soc.
Slover, H.T.; Shelley, L.M. and Burks, T.L. (1967). 69, 119-125.
Identification and Estimation of Tocopherols by Gas
Liquid Chromatography. J. Am. Oil Chem. Soc. 44,
161-166. Recibido: Diciembre 2001
Aceptado: Febrero 2003