ARISTOTLE UNIVERSITY OF THESSALONIKI FACULTY OF SCIENCE DEPARTMENT OF CHEMISTRY Zografia Nystazou Postgraduate work Study of The Effects of Frying

of Sliced Potato on Virgin Olive Oil

Under the supervision of the Associate Professor G. Blekas Laboratory of Chemistry and Food Technology Thessaloniki 2011

OLIVE OIL

"Olive oil" refers to the oil which is obtained from the flesh of the olive of the European variety (Olea europea) exclusively by mechanical means and by physical methods or processes at temperatures that will not cause degradation of the oil.

The olive oil

can be consumed immediately after its reseipt without any pretreatment. In this form, it retains its important components (flavor-aroma).

The olive oil

has been used since the ancient times as a nutrient constituent, as a medicine or a drug carrier and as a cosmetic.

A century ago it was found that the addition of some olive oil in the meal helped in the reduction of the concentration of gastric juices,in the reduction of the indigestion and in the reduction of pain by the taking olive oil with orange juice.

As virgin is characterized the olive oil, which is extracted from the flesh of the olive solely by mechanical or other physical means under conditions particularly thermal conditions, that do not lead to changes, without being subjected to others treatments except for washing with water, the transfusion the centrifugation and the filtration.

The extra virgin olive oil is used as it is for edible purposes and has a perfect taste and aroma. Its acidity can reach 0,8 g/100 g, expressed as oleic acid.

Composition of virgin olive oil in fatty acids

To the triacylglycerols of the olive oil, which are the main lipid fraction, predominantly are found the following fatty acids:

Fatty acids (%) oleic (C18: 1) palmitic (C16: 0), linoleic (C18: 2), stearic (C18: 0), palmitoleic (C16: 1) linolenic (C18: 3). 55 to 83 7.5 to 20 3.5 to 21 0.5 to 5 0.3 to 3.5 <1.0

Components of virgin olive oil with antioxidant activity

The polar phenolic compounds of virgin olive oil are the main antioxidants. When the levels in phenolic compounds exceed 300 mg/kg of oil, the oil may have a bitter taste. However, the high content in polyphenols seems that it is advantageous for the life of the oil, and there is good correlation between the stability and the total content of polyphenols. Amongst various phenolic compounds which were tested for their contribution to stability, the hydroxy-tyrosol and caffeic acid were the most potent antioxidants. In extra virgin olive oil the phenols are calculated in 232 mg / kg.

Some other antioxidants of the olive oil is squalene, alpha-tocopherol and D5-avenasterol.

Use of virgin olive oil as a frying medium for different raw materials

Virgin olive oil shows remarkable resistance to household deep frying of chopped potato or to other use in frying temperatures. In comparison to other vegetable oils, olive oil has a significantly lower rate of change, as was found by measurements of viscosity, total polar components and the loss of tocopherols. This increased stability to thermal oxidation is why this oil can be used in repeated frying before exceeding the limit of discharge , which is about 27% total polar components.

The high resistance to oxidative decomposition is due to its high content of monounsaturated fatty acids and to the presence of minor components with strong antioxidant activity.

In conclusion, olive oil is excellent for applications involving high temperatures. Specifically,

it is rich in monounsaturated and sufficiently low in polyunsaturated fatty acids, particularly linolenic acid, it contains no trans unsaturated fatty acids and it is quite low in saturated fatty acids.

Finally, the olive oil has a sufficiently low freezing point that allows easy absorption from the food being fried, in result the ready-to-eat product contains a small quantity of it.

The methods for controlling the quality of olive oil

1. Gas chromatography

GC (Gas chromatography, GC) is a chromatographic technique which is used among others to assess the composition of fats into fatty acids for more than 50 years.

The fatty acid composition of edible oils mainly is used to assess authenticity, but also to monitor changes occurring during heating of oils.

Prerequisite to assess the composition of an oil in fatty acids is the convertion of its triacylglycerols in methyl esters of its fatty acids.

2. Anisidine value

The determination of the anisidine number is based on the reaction of p-anisidine with volatile and non-volatile aldehydes, which are products of degradation of mainly bound triacylglycerols of fatty acids. The reaction results in the formation of Schiff bases which are yellow and have a maximum absorbance at 350 nm.

During heating of an oil at high temperature, such as frying, the number anisidine is strongly increased. This increase has been associated mainly with the formation of secondary oxidation products.

3. Estimation of the free radical scavenging capacity of olive oil samples with the DPPH assay

The 2,2-diphenyl-1-picrylhydrazyl (DPPH) is a stable radical, which has been used to assess the ability of phenolic compounds which bind free radicals. The higher this is, the stronger the antioxidant activity of the phenolic compound.

The DPPH radical does not dimerize and exist in the monomeric form both in the solid state as dissolved in an organic solvent. Also easily accepts unpaired electrons or hydrogen atoms and hardly oxidized. The solutions of the root are colored, relatively stable, and its concentration in them can be determined by recording the optical absorption in the visible light (515 nm). The optical absorbance of its solutions are stable and independent of the value of the pH, if this is between 5 and 6.5.

4. Polar components

The polar components are products of different reactions including oxidation, hydrolysis and polymerization. Some of these are free fatty acids, aldehydes, di-and monoglycerides and polymerized triglycerides. Generally, polar compounds have been blamed for delay in growth, increase in liver and kidney weight problems and problems in the function of enzymes in animal experiments. Also, some polar compounds are responsible for toxicity and may affect the absorption of triglycerides.

The calculation of the polar components is the best indicator for assessing the quality of an oil, as it refers to all the degradation products of the original triglycerides which are present in the oil. The polymerised triglycerides are the largest group of polar compounds. In most European countries, the limits for disposal and replacement of cooking oil range from 25 to 27% total polar components and 10-16% polymerized triglycerides.

5. Infrared spectroscopy by transformation Fourier (FTIR)

The decomposition of the frying oils leads to changes: at the level of free fatty acids, the color of used oil or the polarity of the oil. Infrared spectroscopy, namely the transformation infrared spectroscopy with Fourier (FTIR) is a method:

less expensive best in performance and easier to use.

Generally it has been used for determining

the content in cis and trans double bonds, the iodine value of the saponification number, the peroxide value, the anisidine number, the content of free fatty acids of the oil samples and the fat and the composition of the food.

EXPERIMENTAL PART
1. Samples

Extra virgin olive oil ELAIS SA. The frying was held at 150oC and 180oC. The ratio of the weight of raw material to the volume of oil: 1/7 and 1/35. Number of successive fryings 10, 20, 30 and 40. Thus 16 samples of olive oil were obtained , 4 for each discrete case of 40 consecutive fryings, whose duration was 4 hours. 10-1/7-150 20-1/7-150 30-1/7-150 40-1/7-150 10-1/7-180 20-1/7-180 30-1/7-180 40-1/7180 10-1/35-150 20-1/35-150 30-1/35-150 40-1/35-150 10-1/35-180 20-1/35-180 30-1/35-180 40-1/35-180

2. Methods
1. There has been convertion of the acylglycerol into methyl esters of fatty acids according to the standard method (IUPAC, 1987). Then a GC analysis of the methyl esters of fatty acids was carried out and from the diagrams of the GC, the ratios of peak areas of the two methyl esters of palmitic acid and linoleic acid were calculated . 2. Also the anisidine value was determined in accordance to the standard method (IUPAC, 1987) and by using the relationship: p-A.V. = 25 x (1.2 As - Ab) / m.

where As is the absorbance of the solution of the oil after the reaction with the solution of panisidine,

Ab is the absorbance of the solution of the oil prior to reaction with the solution of p-anisidine and m is the mass of the oil in g.

3.

The antioxidant capacity with the binding test of the radical of DPPH was estimated and calculated according to the equation:

RSA% = [(A0 - A30) / A0] * 100.

4.

Also the polar components were determined with a financial micromethod and by the relationship cp= [(Ws - Wn) / Ws] * 100

where cp : Percentage of polar constituents ws: The sample weight in mg and wn: The weight of non-polar substances in mg.

5.

Finally the changes in the composition were estimated based on the FTIR spectras measuring the absorbances initially for the estimation of the effect of cooking on cis isomers of the oil in the region 3003 cm-1, whereas for the evaluation of the effect of frying in trans isomers in the region 968 cm-1, corresponding to the bending vibrations of the trans double bond-HC = CH-.

RESULTS
Changes in the ratio of palmitic acid to linoleic acid

Number of fryings

The increase in the ratio was more intense in the case of exposure to high temperature (180oC). More intense change in the ratio EP / EL was observed when the quantity of the raw material which is fried in the same amount of oil was higher (weight ratio of the potato to the volume of oil equal to 1/7) irrespectively to the temperature.

Changes in anisidine value

80 70 60 AnV 50 40 30 20 10 0 0 10 20 30 40 50

1:7 150 1:7 180 1:35 150 1:35 180

The increase in temperature from 150oC to 180oC for a constant weight ratio of potatoes to volume oil had the effect of increasing the number of anisidine.

The increase of the number of anisidine was not observed during the growth of ratio "potato weight to volume oil" while keeping the temperature constant.

The anisidine number of the oil that was not used in frying was equal to 2.5.

Changes in the free radical binding capacity

There is a rapid reduction of free radical binding capacity after only the 10th frying compared to olive oil which is not used in frying (RSA=44%). While at 40th frying the binding capacity of free radicals does not exceed 3%. This suggests rapid destruction of natural antioxidants of virgin olive oil during heating and thus drastical reduction of the the nutritional value.


25 20 TPC% 15 10 5 0 0 10 20 30 40 50

CHANGES IN POLAR COMPOUNDS

1:7 150 1:7 180 1:35 150 1:35 180

What can be observed is that even after 40 fryings the percentage of polar components does not exceed 24-26%, which is a limit for disposal and replacement of the oil in most European countries. The higher rate that was found was 19.6%.

The content of unused oil in total polar components was equal to 2.1%.

Changes in FTIR absorption spectra

The differences that showed the samples of olive oil after frying regardless of frying conditions were as to the intensity of all their absorptions very small.

The results of the reactions occurring are the reduction of the absorption due to components with cis double bonds in their molecule and the increase of the absorption which is due to components with trans double bonds in their molecule. For this reason there was a separate identification of absorption in the range of 3003 cm-1 due to stretching vibrations of cis double bonds, and of the absorption in the region of 968 cm-1 due to vibrations of bending of trans double bonds.

Changes in absorption in region of 3003 cm-1

All the samples that were taken after the 20th frying showed more intensive absorption than the samples that were taken after the 10th frying, regardless the frying conditions.

The samples that were taken after the 30th frying, except for the sample 1/7-150, showed weaker absorption than the samples that were taken after the 40th frying, in contrast to expectations.

It is also noteworthy that the samples that were taken after 10 and 40 fryings showed almost the same intensity of absorption.

Changes of absorption in the region of 968 cm-1

The samples that were taken after the 40th frying showed more intensive absorption than the samples that were taken after the 10th , the 20th and the 30th frying, except for the sample 1/7150.

The other samples that were taken after the 20th frying showed more intensive absorption than the samples that were taken after the 10th and the 30th frying, in contrast to the expectations.

It is also noteworthy that the samples that were taken after 10 and 30 fryings showed an absorption with nearly equal intensity.

CONCLUSIONS-FUTURE WORKThe main conclusions from all the experiments are:

The most critical parameter for the extent of the changes, which were observed in the composition of the olive oil, was the temperature.

The olive oil even after the 40th successive frying (refers to a total duration of successive frying equals to 4 h) could be reused as found in the proportions of polar components.

The olive oil sample after the 10th successive frying had lost the ability to bind free radicals at a rate higher than 60%. This loss indicates that the nutritional benefits of extra virgin olive oil are lost and only the thermal stability remains.

It would be interesting to research for other absorptions in the infrared spectra of used virgin olive oil for frying chopped potato, which allow correlation of their intensity with the content in whole or individual polar components or sub-classes of products of hydrolysis, oxidation and / or polymerization.

In the future the changes in the concentration of both alpha-tocopherol and the total polar phenolic compounds, and other minor components of virgin olive oil, could be also studied in the use of this oil as mediumof heat transfer in the continuous frying of chopped potatoes for an hour the most.

Thank you very much