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Conjugated linoleic acid (CLA) that is commonly found in dairy and ruminant fats, is geometrical and
positional isomer of linoleic acid (LA). Edible oils are not good sources of CLA. Attempts have been made to generate
CLA in edible oils through photoisomerization procedures. CLA isomers have several proven health benefits. This
article reviews procedures for producing CLA containing edible oils by photoisomerization approach and applications
of photoisomerized oils for food uses. The article reviews (1) the photoisomerized production of CLA containing oils
on lab scale, with customized equipment, at pilot plant scale; (2) the effects of iodine content, photoisomerization time,
refining, interference from minor components of oils, efficacy of different edible oils containing LA, interference from
antioxidants; (3) the chemical kinetics, oxidative stability; and (4) photoisomerized oils for frying oils and as drying
oils.The review also briefly covers methods of measurement of CLA.
Abstract:
Introduction
The cis-9, trans-11 conjugated linoleic acid (CLA) is the principal CLA in dairy and meat products and is found mainly in phospholipids fraction (Ha and others 1987; Chin and others 1992).
The amount of cis-9, trans-11 CLA in meat varies from 0.17 to
0.65 g for 100 g of meat-fat whereas the amount of linoleic acid
(LA) found in meat is 0.6 to 1.37 g (Fritsche and Fritsche 1998).
The CLA has positive health effects, such as acting as anticarcinogen (Ip and others 1991), antimutagen (Pariza and others
1979), protecting against immune-induced muscle wasting (Cook
and others 1993; Miller and others 1994), decreasing body fat and
increasing lean body mass (Chin and others 1994; Park and others
1997), and decreasing atheroscelorosis (Lee and others 1994; Nicolosi and others 1997). Photoisomerized soybean oil that contains
25% total CLA of which 70% is contributed by trans, trans CLA
isomers, 25% by cis, trans CLA isomers, were found to decrease
serum cholesterol and serum low density lipoprotein cholesterol,
lowered lipid content, decreased liver weight in obese rats (Gilbert
and others 2011).
Human intake of CLA from dairy lipids and meat fats is onetenth of the needed 3 g/d minimum value extrapolated from
animal studies for beneficial effects (Ip and others 1994; Ma and
others 1999). This is not possible to achieve from existing dietary
sources for CLA. This underscores the need for increasing CLA
isomers by diversifying the sources for CLA, including CLA containing edible oils and fats. Photoisomerization process could be
utilized to produce CLA in edible vegetable oils and fats, which
is economical and can be used to prepare CLA rich oils in large
amounts.
CLAin relation to LA
CLA is a group of positional and geometrical isomers of octadecadienoic acid (LA) having a conjugated double-bond system
(CCCC) starting at carbon 9, 10, or 11. All configura-
doi: 10.1111/1750-3841.12449
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48% to 59% LA was used for producing CLA rich oil by photoisomerization. In the earlier methods, LA methyl esters (5% to 10%)
or vegetable oils, were dissolved in petroleum ether, benzene, or
carbon disulfide and then exposed to a strong light source in the
presence of iodine as a sensitizer (Julliard and others 1987).
CLA production on lab scale. Approximately 0.59% each of
cis-9, trans-11 CLA and trans-10, cis-12 CLA were produced after
90 h of irradiation of soybean oil in the presence of 0.33% iodine.
Soybean oil was used in native form, molecular iodine (I2 ) was dissolved in oil, and no solvents were used. A high-pressure mercury
lamp was utilized to photoisomerize the soybean oil in the presence of iodine in a 250 mL beaker keeping the lamp, at a height of
45 cm. When the oils samples were not stirred, the low amounts
of CLA production was observed. CLA isomers were not produced in the absence of iodine, or in the absence of light or both.
The lipid oxidation products as determined by attenuated total
reflectance-Fourier transform infrared spectroscopy (ATR-FTIR)
and 1 H NMR were not detected (Gangidi and Proctor 2004).
Customized production of CLA. To further advance earlier
work of Gangidi and Proctor (2004), iodine added to soy oil
samples were placed in customized glassware giving a close contact
for oil with lamp. The glassware consisted of a central space for
lamp surrounded by sealed cylindrical space open at the top and
with magnetic stirrer at bottom. The glassware also has allowance
for water jacket to control and maintain temperature of oil.
Utilizing this glassware setup and stirring of the oil at 20 to
25 C gave approximately 50% conversion of LA into conjugated
LA. Approximately 74% of the CLA isomers were trans, trans configuration. A 3.5% of cis, trans CLA isomers were also formed
and the concentration of these isomers was significantly higher
than that found in animal products (Jain and Proctor 2006). A
0.15% iodine gave higher total CLA when compared to 0.1%
or 0.25% iodine concentration. In addition, 0.1% iodine content
gave higher cis-9, trans-11 CLA and trans-10, cis-12 CLA during
the early stages of photoisomerization. No significant oleic acid
peak reduction was observed suggesting possible minimal conversion of cis oleic acid to trans elaidic acid. However, the minimal
conversion of cis oleic acid to trans elaidic acid needs to be confirmed. Lipid oxidation products were not detected as determined
by gas chromatography-mass spectrometry (GC-MS) headspace
analysis, ATR-FTIR, 1 H NMR. In addition, photoisomerized
soy oil with iodine was bleached with clay to remove iodine, and
resulting bleached oil was comparable with that of the original
edible oil, with higher CLA concentration.
CLA content was found to increase by approximately 15%,
when iodine (0.35%) containing soybean oil was 1st added, followed by photoisomerization for 12 h, and later iodine was
removed by adding 5% magnesol (an iodine and polar material
adsorbent). Another dose of iodine (0.35%) added and then photoisomerized for further 12 h resulted in a higher CLA content
of approximately 17.5%. CLA content (approximately 25%) was
also found to increase by 67% when magnesol adsorbent alone
without addition of iodine was utilized to remove iodine (Yettella
and others 2013).
More rapid and near complete conversion of LA into CLA
was observed, when edible oil is solubilized in a nonpolar solvent
and then photoisomerized. A 11% soybean oil in hexane with
0.04% iodine in mixture, resulted in 99% conjugation in approximately 8 h photoisomerization at 70 to 80 C with high pressure
sodium vapor lamp. Approximately 5%, 23%, and 39% were cis-9,
trans-11 CLA; trans-10, cis-12 CLA; and trans, trans CLA isomers,
respectively (Chintareddy and others 2012). However, this type of
1
3
Sen + hv 3 Sen
(or)
Sen + hv 3 Sen
Sen + LH Sen-H + L
Time taken for photoisomerization reaction could be minimized by increasing/optimizing molecular interaction between
free iodine and double bonds and light for faster production of
CLA content. The photoismerization can be performed done at
atmopsheric pressures; and temperatures between 20 and 55 C
are often utilized. Currently, amount of light energy irradiated and
the wavelength on the sample needs to be standardized. Some of
the lamps utilized for photoisomerization are high-pressure mercury lamps (Seki and others 1998; Gangidi and Proctor 2004),
medium pressure mercury lamps (Jain and Proctor 2006), xenon
lamps (Julliard and others 1987), high-pressure and low-pressure
sodium lamps, and tungsten halogen lamps (Chintareddy and others 2012). A xenon lamp was modified by placing a water container
between xenon lamp and sample to absorb UV radiation (Julliard
and others 1987). Typically mercury lamps contain yellow filters to
concentrate UV lights and these need to be removed for optimium
CLA production (Gangidi and Proctor 2004).
Butene, an alkene, has similar double bond to that found in
fatty acids. Less than 3% of cis butene was converted to trans
butene (Back and Cvetanovic 1963) when it was irradiated with
visible light at 501 nm in the presence of iodine as photosensitizer. This study also suggests that the amount of monounsaturated
trans fats produced by photoisomerization from naturally occuring
cis fats in the oil may be negligible (Jain and Proctor 2006) and
also suggests that free radical mediated 1,4 butadiene structure may
be required for maximum transformation of LA to conjugated
LA. This also indicates that the amount of monounsaturated fatty
acids with trans geometry in any given photoisomerized edible oil,
with approximately 20% oleic acid (Jain and Proctor 2006) will
be less than recommended 1% trans fat limit of the total calorific
energy intake/day/person, set by WHO. This is also less than
Indias FSSAI 10% trans fatty acid limit. Therefore, photoisomerized oil with CLA can be consumed. However, the
amount of trans monounsaturated fatty acids produced need to be
confirmed.
Effect of photoisomerization on other edible oils containing LA content. LA (predominantly cis-9, cis-12 C18:2) is
present in edible oils at following proportions: 67.8% to 83.2% in
safflower oil, 48% to 59% in soybean oil, 48.3% to 74% in sunflower oil, 10% to 24% in mustard oil, 15% to 30% in rapeseed
oil (low erucic acid), 36.9% to 47.9% in sesame oil, 9% to 12% in
palm oil, 12% to 43% in ground nut oil, 3.5% to 21% in olive oil,
1% to 2.5% in coconut oil, 2% in butter, 46.7% to 58.2% in cotton
seed oil, 56% in wheat germ oil, 29% to 41% in rice bran oil, 34%
to 65.6% in corn oil (Codex Standard for named Vegetable Oils,
CODEX STAN 210, 1999).
Safflower oil, soy oil, corn oil, sunflower oil, flaxseed oils were
tested producing CLA from LA by photoisomerization procedure (Gammill and others 2010). Safflower oil produced highest
amounts of total CLA isomers, when the ILFU was utilized, followed by soy oil. ILFU increased the surface area to volume of light
exposure. Flaxseed oil (linseed oil) contained significant amounts
of phospholipids that could inhibit CLA production. Sunflower
oil had the turbidity owing to waxes and sterols that could inhibit
CLA production. Lutein/carotenoids, tocopherols also affected
the CLA production. Refining of these oils before subjecting to
photoisomerization yielded slightly higher amounts of CLA. Soy
oil and safflower oil were found to be best edible oils for CLA production. While sunflower oil did not produce any CLA, flaxseed
oil and corn oil produced lesser than expected amounts of CLA.
Therefore, CLA production is not only dependent on LA content
but also on interference from minor components present in edible oils that may not be removed by alkali refining (Gammill and
others 2010).
Vol. 79, Nr. 5, 2014 r Journal of Food Science R783
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Other Research
Additional details of research work on CLA with 4371 articles are published in various journals between 1979 and July
2013, are available in Univ. of Wisconsin (USA) Web site
(http://fri.wisc.edu/cla.php). Specific and elaborate details on
CLA formation by photoisomerization are presented in book
chapter by Jain and Proctor (2012).
Applications
Application of photoisomerized oil as frying oils. Soybean oil enriched with CLA obtained by photoisomerization was
utilized for frying potato chips. CLA-enriched photoisomerized
soybean oil was prepared from soy oil containing approximately
50% LA by photoisomerizing with 0.1% iodine for 144 h and later
the iodine is removed by adsorption with bleaching clay (Jain and
Proctor 2007b). The CLA-enriched photoisomerized soybean oil
performance was similar to that of original soybean oil. However,
the product fried in CLA rich oil contained significant amounts
of CLA. A cis-9, trans-11 CLA and trans-10, cis-12 CLA content
of oil content in potato chips fried utilizing photoisomerized soy
oil was statistically similar to that of original photoisomerized oil
of 1.75% each. Similarly, total CLA content of oil/lipid in potato
chips fried with photoisomerized soy oil for 175 C for 3 min was
similar to that of the original photoisomerized soy oil of 14.75%.
Frying temperature of 175 C, frying time of 3 min, potato chips,
potato chip thickness of approximately 60 to 100/100 of an inch
did not affect the CLA content, composition of the CLA-enriched
soybean oil, oil/lipid content in potato chips fried with CLA enriched photoisomerized oil. Peroxide values of oil from potato
chips and original photoisomerized CLA enriched soybean oil
were same of about 1 meqO2 /kg of sample. The appearance of
the potato chips fried with soybean oil and CLA-enriched (photoisomerized) soybean oil were similar. Oil content of all potato
chips was approximately 39%.
CLA-enriched soybean oil as drying oil. Conjugated fatty
acids containing oil may be utilized as drying oils. CLA containing
soy oil produced by photoisomerization was found to be equal or
better than linseed oil in drying properties (Chintareddy and others
2012).
Acknowledgments
The authors are very grateful to Council of Scientific and Industrial Research (CSIR), Human Resource Development Group
(HRDG), New Delhi for CSIR Research Associateship. They are
thankful to Director, CSIR-Central Food Technological Research
Inst. (CFTRI, Mysore); and Head of the Lipid Science and Traditional Foods (LSTF) Dept. (CSIR-CFTRI, Mysore) for their
encouragement and support.
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