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International Journal of Food Properties

ISSN: 1094-2912 (Print) 1532-2386 (Online) Journal homepage: https://www.tandfonline.com/loi/ljfp20

Application of FTIR Spectroscopy for Monitoring


the Stabilities of Selected Vegetable Oils During
Thermal Oxidation

A. Rohman & Y.B. Che Man

To cite this article: A. Rohman & Y.B. Che Man (2013) Application of FTIR Spectroscopy for
Monitoring the Stabilities of Selected Vegetable Oils During Thermal Oxidation, International
Journal of Food Properties, 16:7, 1594-1603, DOI: 10.1080/10942912.2011.603874

To link to this article: https://doi.org/10.1080/10942912.2011.603874

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International Journal of Food Properties, 16:1594–1603, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1094-2912 print / 1532-2386 online
DOI: 10.1080/10942912.2011.603874

APPLICATION OF FTIR SPECTROSCOPY FOR


MONITORING THE STABILITIES OF SELECTED
VEGETABLE OILS DURING THERMAL OXIDATION

A. Rohman1,2 and Y.B. Che Man3


1
Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Gadjah Mada
University, Yogyakarta, Indonesia
2
Centre of Research for Fiqh Science and Technology (CFiRST), Universiti
Teknologi Malaysia (UTM), Johor Bahru, Malaysia
3
Halal Products Research Institute, Universiti Putra Malaysia, Serdang, Selangor,
Malaysia

Fourier transform infrared spectroscopy has been developed for rapid monitoring of the
oxidative stabilities of selected vegetable oils, namely corn oil, rice bran oil, soybean
oil, and sunflower oil during thermal treatment at 160◦ C for 120 h. There were several
absorbance changes between non-oxidized and oxidized vegetable oils during thermal oxi-
dation. Peak intensities at 3470, 1655, and 967 cm−1 were increased; meanwhile peak
intensities at 3008 and 722 cm−1 were decreased. The R2 values for the correlation between
the absorbance changes at 3008 cm−1 and the specific absorptivities of conjugated dienes
for corn oil, rice bran oil, soybean oil, and sunflower oil were 0.938, 0.845, 0.978, and 0.824,
respectively. The absorbance changes of Fourier transform infrared spectra at 3008 cm−1
were also correlated with the specific absorptivities of conjugated trienes and p-anisidine
values with the acceptable R2 values. Compared with the conventional technique, the use of
Fourier transform infrared spectroscopy for measurement the thermal oxidative stability has
some advantages, i.e., it is a rapid technique and no sample preparation. In addition, Fourier
transform infrared spectroscopy reduces or eliminates solvents and chemical reagents that
are hazardous to human health or to the environment; therefore, Fourier transform infrared
spectroscopy can support the campaign of “green analytical chemistry.”

Keywords: FTIR spectroscopy, Stability, Thermal oxidation, conjugated dienes, Conjugated


trienes, p-Anisidine values.

INTRODUCTION
The oxidation of fats and oils has been known as a major problem affecting the qual-
ity of edible oils[1] because it can change the flavor and nutritional quality of foods and
produce toxic compounds, all of which can make the foods less acceptable to consumers.
The oxidation products typically include low molecular weight compounds that are volatile
as well as undesirable off-flavor compounds, which take place primarily from the break-
down of unsaturated fatty acids during the lipid autoxidation.[2] The oil stabilities during
storage or upon heating are vital parameters for ensuring that oil has good performance at

Received 21 September 2010; accepted 30 June 2011.


Address correspondence to A. Rohman, Department of Pharmaceutical Chemistry, Faculty of Pharmacy,
Gàdjah Mada University, Yogyakarta 55281, Indonesia. E-mail: abdulkimfar@gmail.com

1594
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1595

elevated temperatures.[3] Vegetable oils undergo extensive oxidative deterioration during


storage, marketing, or heating;[4] therefore, the measurement of oxidative stability of veg-
etable oils and their products is very important in order to determine shelf life, acceptability,
and nutritional quality of edible oils.[5]
Numerous techniques have been used for the assessment of edible oil oxidation,
because oxidation involves several stages, as reviewed by Gray.[6] Such techniques are
organoleptic, chemical methods (peroxide value for monitoring the early stages of oxi-
dation, thiobarbituric acid, conjugated diena, conjugated triena, and anisidine value),
and instrumental techniques using chromatographic and spectroscopic based methods.
Conjugated dienes (CDs) and conjugated trienes (CTs) are often used to measure the pri-
mary oxidation products of hydroperoxide, whereas p-anisidine value (p-AV) is one of the
methods used for the monitoring of secondary oxidation products.[7]
The chemical methods can provide an indication on the oxidation level of vegetable
oils; however, these methods are impractical or too laborious, time consuming, destruc-
tive to evaluated oils, and usually use a number of samples, glass apparatus, and toxic
reagents. Therefore, in order to overcome these drawbacks, numerous new methods have
been proposed to replace or to complement the chemical methods.[8] One of the developed
methods is Fourier transform infrared (FTIR) spectroscopy due to its ability to monitor
certain absorption bands, which changed during oxidation.[9] In food studies, FTIR spec-
troscopy has been used for quantitative analysis of fat in mayonnaise[10] and for analysis of
other nutritional constituents of foods in dairy products, muscle tissue, and cereals.[11] The
objective of this research was to develop a FTIR spectroscopic technique as an alternative
method for the assessment of oxidative stability of selected vegetable oils (corn oil, rice
bran oil, soybean oil, and sunflower oil) by making the relationship between the concen-
tration of CDs, CTs, and p-AV with certain absorbance changes at specific FTIR spectra
regions, which directly related to oxidation products.

MATERIALS AND METHODS


Corn oil (CO), rice bran oil (RBO), soybean oil (SO), and sunflower oil (SFO) were
obtained from a local market in Selangor, Malaysia. All of the reagents and solvents used
in this study were of analytical grade. All oils were stored at −20◦ C until being used for
analysis in order to maintain their freshness.

Sample Preparation
First, 200 ml of CO, RBO, SO, and SFO were placed in a 500 mL beaker and sub-
jected to heating in a conventional oven (Memmert Laboratory, Memmert, Germany). at
160 ± 1◦ C for a period of 120 h. To follow the degradation process of vegetable oils during
the heating period, at each 12-h interval, 5 mL of the oil samples were immediately taken
from the oven and were collected in glass vials. These oils were kept at room temperature
until being cooled and were further subjected to analytical measurements in the same day.

Determination of Iodine Value and Fatty Acid Analysis


Iodine value was determined according to AOCS method Cd 1d-92.[12] The
composition of fatty acids in the studied oils was determined according to Rohman and
Che Man.[13]
1596 ROHMAN AND CHE MAN

Measurement of Conjugated Dienes (CDs) and Conjugated Trienes


(CTs)
CDs and CTs were determined according to the procedure described by Frankel
et al.[14] The oil samples (0.05 g) were accurately weighed into 10-mL volumetric flasks,
dissolved in isooctane, and made up to the mark with the same solvent. The mixtures were
shaken thoroughly and their absorbances were measured for the determination of CDs and
CTs using UV-Vis spectrophotometer U-2810 (Hitachi, Tokyo, Japan) at 234 and 270 nm,
respectively, on a quartz cuvette (1 cm). These absorbances were used for calculating the
specific absorptivity of CDs and CTs.

Determination of p-Anisidin Value (p-AV)


p-AV was determined according to AOCS[10] and Erkan et al.[15] An aliquot of
0.5 g of oil samples was accurately weighed on analytical balance (sensitivity 0.1 mg)
and dissolved with 25 mL of n-hexane. This solution was read using a UV-Vis spectropho-
tometer U-2810 (Hitachi, Tokyo, Japan) against n-hexane as a reference and recorded as
A1 . In another separate run, a 5-mL portion of the sample solutions was mixed with 1 mL
of p-anisidine solution (2.5 g/L glacial acetic acid). Accordingly, a blank solution com-
posed of 5 mL of n-hexane instead of sample solution was prepared. The sample and blank
solutions were kept in the dark at ambient temperature for 10 min and the absorbance of
the sample solution (A2 ) was measured against the blank solution.
p-AV was calculated as follows:

1.2A2 − A1
p − AV = 25 ,
m

where A1 and A2 are the measured absorbancies, as described above; m is the mass of oil.

Measurement of FTIR Spectra


FTIR spectra of non-oxidized and oxidized oil samples were directly recorded at
accessory of attenuated total reflectance (dimension 10 mm × 60 mm) using FTIR spec-
trometer (Nicolet 6700 from Thermo Nicolet Corp., Madison, WI, USA). The oil samples
were directed in good contact with attenuated total reflectance (ATR) at controlled room
temperature (20◦ C). FTIR spectra of oil samples were collected in a frequency region
of 4000–650 cm−1 by co-adding 32 scans and at resolution of 4 cm−1 . All spectra were
rationed against a background of air spectrum. After every scan, a new reference air back-
ground spectrum was taken. These spectra were recorded as absorbance values at each data
point in triplicate. The software Omnic version 6.1 (Nicolet, Madison, WI, USA) was used
to treat and manipulate spectra.

Statistical Analyses
All measurements of CDs, CTs, and p-AV were done in at least three replications.
Data were presented as mean ± standard deviation (SD). Data from chemical and fatty acid
analyses were subjected to analysis of variance (ANOVA) using SPSS version 17 (SPSS
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1597

Inc., Chicago, IL, USA) to identify the differences among means. Statistical significance
was declared at P < 0.05.

RESULTS AND DISCUSSION


Fatty Acid (FA) Compositions
FA composition is one of the factors affecting the oxidation of edible oils, besides oil
processing; energy of light or heat; the concentration and type of oxygen; and the presence
of transition metals, thermally oxidized compounds, pigments, and antioxidants. These fac-
tors interactively affect oil oxidation, and it is not easy to differentiate the individual effect
of these factors.[16] FA compositions, especially monounsaturated fatty acids (MUFA) and
polyunsaturated fatty acids (PUFA) together with iodine values (IV) of evaluated vegetable
oils were shown in Table 1.
Edible oils with high IV, such as SO and CO stored in the dark, showed a significant
shorter induction period than those with low IV.[17] Vegetable oils with more unsaturated
FAs are oxidized more rapidly than less unsaturated ones. If the level of unsaturation rises,
the formation rate and the amount of primary oxidation products will increase.[18] Choe and
Min,[16] in their review, reported that the relative rate of auto-oxidation reactions of oleic,
linoleic, and linolenic acids was as 1:40–50:100, respectively, based on the oxygen uptake.
From Table 1, it can be seen that RBO and SFO were rich in MUFA and had a lower level
of PUFA compared with CO and SO. Meanwhile, SO contained the highest level of PUFA,
which was significantly different from others (P < 0.05). Based on PUFA concentration,
these values suggested that SO is more susceptible to oxidative reaction followed by CO >
SFO > RBO.

FTIR Studies of Non-Oxidized and Oxidized Vegetable Oils


FTIR spectra of non-oxidized oils at mid infrared region (4000–650 cm−1 ) were
shown in Fig. 1. The prominent peaks responsible for IR absorptions with certain vibra-
tion modes were described in our previous paper.[19] During thermal oxidation, there

Table 1 FA composition and IV of studied oils (CO, RBO, SO, and SFO).†,‡

FAs CO RBO SO SFO

C14:1 0.04 ± 0.00 0.01 ± 0.00 0.01 ± 0.00 0.01 ± 0.00


C16:1 0.10 ± 0.01 0.19 ± 0.01 0.10 ± 0.00 0.03 ± 0.00
C18:1 27.48 ± 0.18 41.49 ± 1.28 21.61 ± 0.76 37.52 ± 1.77
C20:1 0.42 ± 0.00 0.46 ± 0.02 0.39 ± 0.02 0.40 ± 0.02
MUFA 28.04b 42.15d 22.11a 37.96c
C18:2 53.13 ± 0.69 32.38 ± 0.38 52.97 ± 0.70 47.69 ± 0.24
C18:3 0.72 ± 0.02 0.76 ± 0.02 6.72 ± 0.05 0.21 ± 0.01
C20:2 0.24 ± 0.02 0.45 ± 0.05 0.21 ± 0.02 0.01 ± 0.00
PUFA 54.09c 33.59a 59.90d 47.91b
Iodine value 125 ± 0.72c 102 ± 0.35a 134 ± 1.08d 106 ± 0.65b
† Each value in the table represents the means from at least triplicate analysis; SD is given in after ±; MUFA:

monounsaturated fatty acid; PUFA: polyunsaturated fatty acid; IV: iodine value.
‡ Different letters within each row are significantly different at P < 0.05. CO: corn oil; RBO: rice bran oil; SO:

soybean oil; SFO: sunflower oil.


1598 ROHMAN AND CHE MAN

Figure 1 FTIR spectra of non-oxidized oils (corn oil, rice bran oil, soybean oil, and sunflower oil) measured at
frequency 4000–650 cm−1 . (Color figure available online.)

Figure 2 FTIR spectra changes of CO during heating for 120 h. The increase and decrease of absorbency at
certain frequencies were assigned with arrows (↑ = increased; ↓ = decreased). (Color figure available online.)

were several FTIR spectral changes of CO, RBO, SO, and SFO at mid infrared region
(3600–650 cm−1 ). Figure 2 is an example of FTIR spectra change of corn oil during thermal
oxidation at 160◦ C up to 120 h.
The peak intensities at 722 cm−1 were decreased, caused by the loss of cis double
bonds; meanwhile, the increase of trans double bonds during thermal oxidation can be
observed by increasing peak intensities at 967 cm−1 . The increase of another peak can
be seen in regions of 1744 and 1655 cm−1 , which is due to the formation of carbonylic
compounds and cis allylic during thermal oxidation. Two peaks at 2853 and 2923 cm−1
remained nearly unaffected. The peak at 3008 cm−1 was decreased because of the decrease
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1599

of cis allylic (C=CH) bonds. Finally, a low absorbance increase was observed around
3470 cm−1 , corresponding to the formation of hydroxyl group (-OH) formed during thermal
oxidation.[9]

The Specific Absorptivity Values of CDs and CTs of Vegetable Oils


The determination of CDs and CTs values in unsaturated lipids is a sensitive assay,
but the magnitude of changes in absorption is not easily related to the extent of oxidation.
However, during the early stages of oxidation, the increase in UV absorption due to the
formation of CDs and CTs is proportional to the uptake of oxygen and to the generation of
peroxides. Therefore, the content of CDs and CTs can serve as a relative measurement of
oxidation.[20] The contents of CDs and CTs were expressed with the specific absorptivity
values of CO, RBO, SO, and SFO. Generally, the specific absorptivity values of CDs
were increased during the course time of oxidation, as shown in Table 2. There was a
significant different (P < 0.05) of all CDs values during thermal treatments for CO and
SO; meanwhile, no significant differences were observed during 36 and 48 h as well as
during 96 and 108 h for RBO. For SFO, the CDs values were not significantly different for
60 and 72 h, 84 and 96 h, and for 108 and 120 h at significance level of 0.05. The highest
increase of CDs was observed in SO. The increase of CDs values was in agreement with
the contents of PUFA as shown in Table 1 with the order of SO > CO > SFO > RBO.
The specific absorbtivity values of CDs were further correlated with absorbance changes
at peak region of 3008 cm−1 in order to obtain the relationship for both parameters.
A peak at 3008 cm−1 correlates with the decrease of unsaturation of cis double bonds;[19]
meanwhile, CDs can be thought of as the formation of conjugated double bonds because
of the oxidation processes.
Figure 3 showed the linear regression for the relationship between the absorbance
changes at 3008 cm−1 (x-axis) and specific absorptivity values of CDs (y-axis) in CO. The
equations for such relationship obtained for other oils are y = −528.8x + 143.6, R2 =
0.845 (RBO); y = −347.1x + 114.4, R2 = 0.9785 (SO); and y = −167.4x + 69.04, R2 =
0.824 (SFO). The slope values obtained for all equations were negative, meaning that there
was an inverse relationship for both parameters. The coefficients of determination (R2 ) for

Table 2 The specific absorptivity values of CDs of CO, RBO, SO, and SFO during thermal oxidation
for 120 h.†,‡

Time CO RBO SO SFO

0 7.81 ± 0.08a 5.37 ± 0.11a 6.67 ± 0.08a 6.52 ± 0.07a


12 14.13 ± 0.14b 7.80 ± 0.12b 12.97 ± 0.11b 13.52 ± 0.02b
24 18.59 ± 0.13c 12.73 ± 0.12c 18.35 ± 0.20c 20.31 ± 0.05c
36 18.76 ± 0.09d 16.63 ± 0.19d 22.47 ± 0.14d 20.78 ± 0.04d
48 21.39 ± 0.14e 16.97 ± 0.10d 23.37 ± 0.17e 22.97 ± 0.19e
60 26.07 ± 0.16f 22.06 ± 0.15e 29.25 ± 0.13f 29.22 ± 0.16g
72 27.28 ± 0.14g 23.84 ± 0.17f 34.09 ± 0.15g 29.23 ± 0.16g
84 28.09 ± 0.21h 24.68 ± 0.13g 36.49 ± 0.18h 30.03 ± 0.17f
96 29.23 ± 0.38i 29.59 ± 0.20h 41.41 ± 0.15i 30.20 ± 0.23f
108 33.10 ± 0.48j 30.05 ± 0.34h 42.89 ± 0.21j 31.93 ± 0.24h
120 35.88 ± 0.24k 30.86 ± 0.19i 47.12 ± 0.26k 32.24 ± 0.14h
† Each value in the table represents the means of triplicate analysis; SD is given in after ±.
‡ The same letters within each column are not significantly different at P < 0.05.
1600 ROHMAN AND CHE MAN

Figure 3 The relationship between absorbance changes at 3008 cm−1 and CDs values of corn oil. (Color figure
available online.)

such correlation of studied oils were in the range of 0.824–0.978, indicating that a linear
relationship exists for both parameters. These results suggested that the absorbance changes
at 3008 cm−1 can be proposed as a stability index for lipid-containing foods.
Table 3 compiled the specific absorptivity values of CTs of CO, RBO, SO, and SFO
during thermal treatment at 160◦ C for 120 h. As CDs values, the similar modes were
observed for CTs. An increase of CTs values was observed for the studied vegetable oils
during thermal oxidation. It can be stated that the conjugated trienoic systems were devel-
oped during thermal oxidation. Among the studied oils, SO exhibited the highest increase
of CTs values during oxidation for 120 h, followed by SFO, CO, and RBO. The CTs values
were not significantly different at 48 and 60 h, 24 and 36 h, as well as 36 and 48 h at a
significance level of 0.05, for CO, RBO, and SO. In SFO, there is no significant difference
(P = 0.05) during thermal oxidation between 36 and 48 h, 60 and 72 h, as well as between
84 and 96 h.
In order to propose that absorbance changes at 3008 cm−1 can be used as an alterna-
tive method for the measurement of CTs values rather than conventional technique using

Table 3 The specific absorptivity values of CTs of CO, RBO, SO, and SFO during thermal oxidation.†,‡

Time CO RBO SO SFO

0 3.81 ± 0.04a 2.59 ± 0.05a 2.51 ± 0.03a 2.49 ± 0.01a


12 4.45 ± 0.05b 4.07 ± 0.03b 4.53 ± 0.02b 6.53 ± 0.05b
24 5.03 ± 0.08c 4.76 ± 0.03c 4.80 ± 0.04c 7.16 ± 0.03c
36 5.18 ± 0.03c 5.29 ± 0.05d 6.28 ± 0.06d 7.39 ± 0.03d
48 5.91 ± 0.06d 5.99 ± 0.04e 6.33 ± 0.02d 7.44 ± 0.03d
60 6.23 ± 0.13e 6.13 ± 0.02e 7.57 ± 0.05e 7.66 ± 0.08e
72 6.78 ± 0.05f 6.52 ± 0.08f 7.98 ± 0.05f 7.81 ± 0.06e
84 7.37 ± 0.08g 7.49 ± 0.05g 8.34 ± 0.09g 8.14 ± 0.12f
96 8.10 ± 0.11h 7.81 ± 0.06h 8.72 ± 0.07h 8.15 ± 0.07f
108 8.64 ± 0.05i 8.05 ± 0.05i 9.31 ± 0.08i 8.43 ± 0.04g
120 9.30 ± 0.15j 8.25 ± 0.11i 9.86 ± 0.08j 9.53 ± 0.12h
† Each value in the table represents the means of triplicate analysis; SD is given after ±.
‡ The same letters within each column are not significantly different at P < 0.05.
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1601

spectroscopic UV, the relationship between absorbance changes at 3008 cm−1 (x-axis) and
CTs values (y-axis) was built. The equations obtained were as follows: y = −54.91x +
21.64, R2 = 0.993 (CO); y = −104.8x + 30.57, R2 = 0.829 (RBO); y = −60.06x + 21.77,
R2 = 0.964 (SO); and y = −22.56x + 13.62, R2 = 0.887 (SFO). From these equations and
taking into account the R2 values, FTIR absorbance changes at 3008 cm−1 can be an alter-
native method for the determination of CTs due to its capability to provide good linearity
between absorbance changes and CTs values.

p-Anisidine Value (p-AV)


Table 4 listed p-AVs of these vegetable oils during thermal oxidation for 120 h. For
all vegetable oils evaluated, p-AV increased as a function of temperature treatments. The
initial p-AV of SO was the highest among others, however, at the last treatment, SO has
not appeared yet to be the highest p-AV compared with RBO and CO. This phenomenon
may be explained by the presence of some natural antioxidants, such as tocopherol and
phenolics compounds, in the used SO, which is much more compared to those in RBO
and CO.
Furthermore, in order to make the relationship between FTIR absorbance changes
and p-AV, a linear regression was built for such a purpose. Peak changes at 1654 cm−1 were
chosen for making the relationship between absorbance changes (x-axis) at 1654 cm−1 and
p-AV (y-axis). This peak directly attributed to cis double bonds (olefinic group) formed dur-
ing thermal oxidation.[9] In addition, p-AV measured double bonds in studied oils produced
during thermal oxidation. For this reason, this frequency was further used as an indication
of the addition of a double bond due to oxidation. The equations obtained were: y = 7486x
– 675.2, R2 = 0.724 (CO); y = 4291x – 327.4, R2 = 0.782 (RBO); y = 5325x – 479.4, R2 =
0.799 (SO); and y = 1.656x – 125.5, R2 = 0.826 (SFO).
The R2 values obtained for the relationship between absorbance changes at
1654 cm−1 and p-AVs were not high enough (0.724–0.826), therefore, another absorbance
change was preferred to be correlated with p-AVs. Frequency at 3008 cm−1 is related to
the reduction of cis-allylic bonds; meanwhile, p-AV indicates the formation of 2-alkenals,
which has double bonds in its structure. For this reason, the absorbance changes at this

Table 4 p-AVs of CO, RBO, SO, and SFO heated at a high temperature of 160◦ C for 120 h.

Time CO RBO SO SFO

0 3.80 ± 0.38a 1.95 ± 0.26a 4.60 ± 0.23a 3.20 ± 0.48a


12 41.50 ± 0.53b 16.50 ± 0.40b 21.00 ± 2.08b 30.00 ± 0.40b
24 50.50 ± 2.03c 33.10 ± 0.46c 18.20 ± 0.46b 30.05 ± 0.57b
36 57.70 ± 0.53d 39.35 ± 0.88d 31.35 ± 1.04c 37.65 ± 0.84c
48 63.55 ± 1.65e 44.80 ± 0.69e 42.15 ± 1.30d 41.05 ± 0.09c
60 68.35 ± 0.53f 48.50 ± 0.46f 58.05 ± 0.79e 40.35 ± 1.59c
72 82.90 ± 1.08g 56.80 ± 1.16g 59.15 ± 1.65e 63.10 ± 1.86d
84 94.00 ± 0.75h 61.05 ± 0.94h 63.50 ± 0.34f 70.25 ± 0.46e
96 104.60 ± 0.31i 64.85 ± 1.12i 78.35 ± 0.31g 74.60 ± 2.33e
108 120.95 ± 0.48j 104.11 ± 1.11j 93.25 ± 0.68h 83.85 ± 0.79f
120 128.50 ± 2.73k 118.95 ± 1.95k 96.75 ± 0.91i 86.95 ± 3.32f
† Each value in the table represents the means of triplicate analysis; SD is given after ±.
‡ The same letters within each column are not significantly different at P < 0.05.
1602 ROHMAN AND CHE MAN

frequency were subsequently used to be correlated with p-AV. The equations obtained from
the relationship between absorbance changes at 3008 cm−1 (x-axis) and p-AVs (y-axis) of
evaluated vegetable oils are as follows: y = −1113.0x + 382.7, R2 = 0.952 (CO); y =
−1836.0x + 483.0, R2 = 0.844 (RBO); y = −796.8x + 248.4, R2 = 0.922 (SO); and y =
−173.2x + 237.7, R2 = 0.948 (SFO).
Based on the R2 values obtained, the absorbance changes at 3008 cm−1 were chosen
to be correlated with p-AV because of the higher R2 values obtained compared with those
at a frequency of 1654 cm−1 . These results suggested that measurements of absorbance
changes at 3008 cm−1 can be used as an alternative technique for the determination
of p-AV.

CONCLUSION
The application of FTIR spectroscopy as an alternative technique for measuring the
oxidative stabilities of edible oils can overcome some drawbacks when using chemical anal-
ysis, such as time consuming, destructive to the evaluated oils, involvement of the number
of samples, glass apparatus, toxic solvents, and hazardous reagents, which are harmful to
human health and to the environment. During thermal oxidation, absorbance changes at a
frequency region of 3008 cm−1 can be used to measure the conjugated dienes (CDs) and
trienes (CTs) as well as p-anisidine value.

ACKNOWLEDGMENTS
The first author wishes to thank The Directorate for Higher Education (Dikti), The Ministry
of National Education, Republic of Indonesia, for the scholarship during his Ph.D. program in
Halal Products Research Institute, UPM, Malaysia. The authors also wish to thank the Ministry of
Science, Technology, and Innovations (MOSTI), Malaysia for providing the funding support awarded
to Professor Dr. Yaakob B. Che Man.

REFERENCES
1. Velasco, J.; Dobarganes, C. Oxidative stability of virgin olive oil. European Journal of Lipid
Science and Technology 2002, 104, 661–676.
2. Reische, D.W.; Lillard, D.A.; Eitenmiller, R.R. Antioxidants. In: Food Lipids: Chemistry,
Nutrition, and Biotechnology; Akoh, C.C.; Min, D.B.; Eds.; Marcell Dekker: New York, 2002;
479–516.
3. Hemalatha, G. Sesame lignans enhance the thermal stability of edible vegetable oils. Food
Chemistry 2007, 105, 1076–1085.
4. Smith, S.A.; King, R.E.; Min, D.B. Oxidative and thermal stabilities of genetically modified high
oleic sunflower oil. Food Chemistry 2007, 102, 1208–1213.
5. Sherwin, E.R. Oxidation and antioxidants in fat and oil processing. Journal of the American Oil
Chemists’ Society 1978, 55, 809–814.
6. Gray, J.I. Measurement of lipid oxidation: A review. Journal of the American Oil Chemists’
Society 1978, 55, 539–546.
7. Abuzaytoun, R.; Shahidi, F. Oxidative stability of flax and hemp oils. Journal of the American
Oil Chemists’ Society 2006, 83, 855–861.
8. Yildiz, G.; Wehling, R.L.; Cuppett, S.L. Monitoring PV in corn and soybean oils by NIR
spectroscopy. Journal of the American Oil Chemists’ Society 2002, 79, 1085–1089.
MONITORING OXIDATIVE STABILITY USING FTIR SPECTROSCOPY 1603

9. Muik, B.; Lendl, B.; Molina-Dıaz, A.; Ayora-Canada, M.J. Direct monitoring of lipid oxidation
in edible oils by Fourier transform Raman spectroscopy. Chemistry and Physics of Lipids 2005,
134, 173–182.
10. Chippie, A.L.; Jamieson, P.R.; Golt, C.M.; Hsu, C.-H.; Lo, Y.M. Quantitative analysis of fat and
moisture in mayonnaise using Fourier transform infrared spectrometer. International Journal of
Food Properties 2002, 5, 655–665.
11. Kulmyrzaev, A.A.; Karoui, R.; De Baerdemaeker, J.; Dufour, E. Infrared and fluorescence spec-
troscopic techniques for the determination of nutritional constituents in foods. International
Journal of Food Properties 2007, 10, 299–320.
12. AOcs. 1996. Official and Tentative Methods, 5th Edition; American Oil Chemists’ Society:
Champaign, IL.
13. Rohman, A.; Che Man, Y.B. Monitoring of virgin coconut oil (VCO) adulteration with palm oil
using Fourier transform infrared (FTIR) spectroscopy. Journal of Food Lipids 2009, 16, 618–628.
14. Frankel, E.N.; Huang, S.W.; Kanner, J.; German, J.B. Interfacial phenomena in the evaluation
of antioxidants: Bulk oils vs. emulsions. Journal of Agricultural and Food Chemistry 1994, 42,
1054–1059.
15. Erkan, N.; Ayranci, G.; Ayranci, E. A kinetic study of oxidation development in sunflower oil
under microwave heating: Effect of natural antioxidants. Food Research International 2009, 42,
1171–1177.
16. Choe, E.; Min, D.B. Mechanisms and factors for edible oil oxidation. Comprehensive Reviews
in Food Science and Technology 2006, 5, 169–186.
17. Tan, C.P.; Che Man, Y.B.; Selamat, J.; Yusoff, M.S.A. Comparative studies of oxidative stability
of edible oils by differential scanning calorimetry and oxidative stability index methods. Food
Chemistry 2002, 76, 385–389.
18. Martin-Polvillo, M.; Marquez-Ruiz, G.; Dobarganes, M.C. Oxidative stability of sunflower oils
differing in unsaturation degree during long-term storage at room temperature. Journal of the
American Oil Chemists’ Society 2004, 81, 577–583.
19. Rohman, A.; Che Man, Y.B. Fourier transform infrared (FTIR) spectroscopy for analysis of extra
virgin olive oil adulterated with palm oil. Food Research International 2010, 43, 886–892.
20. Pegg, R. Lipid oxidation stability. In: Wrolstad R.E. et al. (ed), Handbook of Food Analytical
Chemistry: Water, Proteins, Enzjmes, Lipids, and Carbohydrates; Wrolstad, R.E., Acree, T.E.;
Decker, E.A.; Penner, M.H.; Reid, D.S.; Schwartz, S.J.; Shoernaker, C.F.; Smith, D.; Sporns, P.;
Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, 2005; 513–547.

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