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The antioxidant effects of sesamol lms were evaluated using a food simulant (linoleic acid) and a real food
(oat cereal). Sesamol was melt blended with high density polyethylene, linear low density polyethylene and
ethylene-vinyl acetate resins using co-extrusion to produce sesamol lms of multilayer structure; for
comparison, lms containing butylated hydroxytoluene (BHT) or no additive (as control) were also produced.
At least 60% of the initial amount of sesamol remained in the lms after extrusion. The release of sesamol
from the sesamol lms was about six times faster at 30 C than at 10 C. The antioxidant effectiveness of
sesamol and BHT was evaluated on the basis of induction period of lipid oxidation, conjugated dienes (for
linoleic acid), hexanal (for oat breakfast) and sensory evaluation. Compared with the control lm, the sesamol
lms extended the induction period of linoleic acid by ve and eight times at 40 C and 23 C, respectively.
After 12 month storage at 23 C, hexanal formation was 59% less in cereal packaged with sesamol lms than
that packaged with control lm. Rancid odours were detected in cereal packaged with control lms, but not
with sesamol or BHT lms. The incorporation of sesamol had only slight effects on tensile properties and
transparency. Copyright 2012 John Wiley & Sons, Ltd.
Received 9 January 2012; Revised 26 January 2012; Accepted 13 February 2012
KEY WORDS: sesamol; lipid oxidation; controlled release packaging
INTRODUCTION
Lipid oxidation is a major deterioration mode limiting shelf lives of fat-containing foods. This free
radical chain reaction, once started by initiators such as light and metal, keeps itself going indenitely
in a series of hydrogen abstraction that can potentially involve hundreds of lipid molecules from a
single initiation.1 Alkoxyl radicals from decomposition of intermediate hydroperoxides undergo
scission reactions and form aldehydes and ketones that are responsible for the characteristic rancid
off-odours and avours of rancid products. Reactions of lipid free radicals and secondary oxidation
products with proteins and other food components degrade functionality, cause loss of nutritional
value and even generate toxic compounds,2 all of which shorten the shelf life of food products.35
To inhibit lipid oxidation, antioxidants are traditionally added into food formulation to quench lipid
free radicals, stop chain reactions and extend shelf life.4
An innovative technology for adding an antioxidant into food using the package as a delivery system is
known as controlled release packaging (CRP)5 in which the antioxidant is incorporated into the package
and then released onto the food surface, where most lipid oxidation occurs, in continually replenished
small amounts to retard lipid oxidation.6 For a volatile antioxidant, the release involves the sequential
steps of diffusion of the antioxidant through the polymer bulk phase toward the polymer surface,
* Correspondence to: Kit Yam, Department of Food Science, School of Environmental and Biological Sciences, Rutgers,
The State University of New Jersey, 65 Dudley Rd., New Brunswick, NJ 089018520, USA.
E-mail: yam@aesop.rutgers.edu
Copyright 2012 John Wiley & Sons, Ltd.
32
X. ZHU ET AL.
evaporation of the antioxidant from the polymer surface to the package headspace and sorption of the
antioxidant onto the food surface.
Butylated hydroxytoluene (BHT) is a synthetic volatile antioxidant that has long been added to
packages of dry foods such as breakfast cereal.7,8 However, the current trend is to replace BHT and
other potentially toxic synthetic additives with natural compounds, as the society prefers natural
products and greener labels.8 Sesamol, an important component from sesame seed and oil, is a potent
antioxidant with chemical structure (Figure 1) containing a benzodioxole group responsible for solubility
and a phenolic group responsible for antioxidant activity.9 Sesamol has been shown to be a highly
effective antioxidant for inhibiting oxidation in lard10 and food oils11 and for stabilizing oils against
thermal degradation during frying12 and microwave heating.13 It has been shown that 100 mg/kg sesamol
and tocopherol reduced lipid oxidation and irradiation-induced off-avours in ground beef14 and 200 mM
sesamol stabilized irradiated pork homogenates and patties.15 Because sesamol is a highly effective
natural antioxidant, relatively inexpensive and available compared with other natural antioxidants,
it is a good candidate to replace synthetic antioxidants such as BHT in CRP applications.
The objective of this study was to evaluate the antioxidant effectiveness of sesamol lms to inhibit lipid
oxidation in packaged foods. To achieve this objective, the following tasks were performed: (a) determine
the release kinetics of sesamol from the polymer lms into headspace, (b) evaluate the antioxidant
effectiveness of sesamol lms on a food simulant (linoleic acid) and a real food (oat-based breakfast
cereal), and compare it with those of the control (no antioxidant) and BHT lms and (c) evaluate the
effects of incorporating sesamol on the tensile properties and transparency of the lms.
MATERIALS AND METHODS
Materials
Barefoot resins (containing minimum plastics additives) of high-density polyethylene (HDPE), linear
low-density polyethylene (LLDPE) and ethylene-vinyl acetate (EVA) were provided by Berry Plastics
(Chippewa Falls, WI, USA). BHT (99%), hexanal (99%) and 2-methyl-pentanal (98%) were purchased
from Sigma-Aldrich Co. (Milwaukee, WI, USA). Sesamol (98%), linoleic acid (99%) and all organic
solvents (high-performance liquid chromatography grade) were purchased from Fisher Scientic
Inc. (Suwanee, GA, USA). A commercial oat-based cereal was supplied by a major food company,
not named for condentiality reason. The cereal contained only endogenous antioxidants with no
additional antioxidants in the formulation.
Film production
Sesamol resin concentrates were prepared by melt blending sesamol with LLDPE, HDPE and EVA
resins using a twin-screw extruder. The resin concentrates were then dry mixed with appropriate
amounts of virgin resins using a ribbon mixer to dilute the sesamol concentration to 1000 or
2000 mg/kg. The lms in Table 1 were produced using a co-extruder (Davis-Standard, Pawcatuck,
CT, USA) operating at a die temperature of 221 C and a screw speed of 70 rpm. Films containing
no antioxidant (as control) and BHT were also produced for comparison purpose. The lm structures
are shown in Figure 2 in which the thickness ratio of the three layers was approximately 20/60/20.
33
Table 1. Extractable antioxidants and layer structures of lms used in this study.
Film
A
B
C
Antioxidant
Extractable
antioxidant (mg/kg)
Sesamol
Sesamol
BHT
2000
1000
2000
1218 11
646 18
1606 29
LLDPE/HDPE/HDPE
HDPE/HDPE/EVA
HDPE/HDPE/EVA
Film A
Film B
Film C
LLDPE
HDPE
HDPE
HDPE+sesamol
HDPE+sesamol
HDPE+BHT
HDPE
EVA
EVA
sesamol film
linoleic acid
Figure 3. Experimental setup for testing antioxidant effect of sesamol lms on linoleic acid.
Copyright 2012 John Wiley & Sons, Ltd.
34
X. ZHU ET AL.
incubated in an environmental chamber (C25KC, New Brunswick Scientic Inc., New Brunswick,
NJ, USA) at 10 C and 30 C in the dark and were periodically removed for analysis. One gram
lm sample from each square lm was cut out, and the amount of sesamol retained in the
lm was measured by the method of solvent extraction mentioned previously. The amount of
sesamol released was calculated by subtracting the amount of retained sesamol from the initial
sesamol in the lm.
Antioxidant effect of sesamol lms on linoleic acid as food simulant
The experimental setup shown in Figure 3 (adopted from Jongjarionrak and Nerin)17,18 was used to test
the effect of released sesamol on inhibiting lipid oxidation in a food simulant, linoleic acid. One gram of
lm A and control lm (with no antioxidant) was hung in a 1 l sealed jars containing 10.0 g linoleic
acid stored in dark at 23 C and 40 C. The linoleic acid was periodically sampled and diluted with
cyclohexane, and the extent of oxidation in it was determined by quantifying conjugated dienes measured
optically at 234 nm using a spectrophotometer (UV-1700 UVVis spectrophotometer, Shimadzu Co.,
Kyoto, Japan). Molar concentrations of dienes were calculated using an absorption coefcient of
26 000 l/mol cm.19,20 The length of the induction period (time at which active oxidation commenced)
was used as an index to evaluate the antioxidant effect of sesamol lms.21,22
35
Figure 4. Release prole of sesamol; = sesamol release at 30 C and = sesamol release at 10 C.
Copyright 2012 John Wiley & Sons, Ltd.
36
X. ZHU ET AL.
0.450
0.400
0.350
0.300
0.250
0.200
0.150
0.100
0.050
0.000
0
6
8
Time (days)
10
12
14
0.450
0.400
0.350
0.300
0.250
0.200
0.150
0.100
0.050
0.000
0
10
20
30
40
Time (hrs)
50
60
70
Figure 5. Effect of sesamol lm on formation of conjugated dienes in linoleic acid at 23 C (A) and
40 C (B); = control and = sesamol lm.
Antioxidant effect of sesamol and BHT lms on oat cereal
Figure 6 shows the hexanal concentrations in the cereal pouches estimated using the SPME method.
Although this method might not provide absolute values for hexanal concentrations, it is sufcient
to indicate the relative concentrations of hexanal among the samples for comparison purpose.
After 1 year of storage at 23 C in dark, cereal packed in different lms showed distinctly different
hexanal concentrations, an indicator of lipid oxidation.28 Hexanal levels were 85% lower in the BHT
pouches and 59% lower in the sesamol pouches than that in the control pouches (p < 0.05) (Figure 6).
Because the amount of sesamol was less than half the amount of BHT in the pouches, the antioxidant
effectiveness of BHT and sesamol pouches were comparable. The informal sensory evaluation
concluded that no off-odours were detected in the BHT or sesamol pouches, while strong rancid odour
was detected in the control pouches. This shows that even though the antioxidants volatilized from the
Figure 6. Hexanal concentration extracted by SPME in cereal packaged by different lms after 1 year
of storage.
Copyright 2012 John Wiley & Sons, Ltd.
37
Table 2. Mechanical and optical properties of lms with and without antioxidants.
Controls (no antioxidant)
Film A
Film B/C
Film B
Film C
packaging lms within hours, the effect continued for an extended period. The BHT and sesamol
samples were indistinguishable by taste and odour after 1 year, suggesting that sesamol may be an
effective alternative to BHT for stabilizing cereal products.
Physical properties
Table 2 shows that there are slight variations in thickness of the lms produced, which is common for
lm production. When these variations are taken into account, the data show that the addition of
sesamol or BHT has slight or no practical impact on the tensile and optical properties.
CONCLUSION
Sesamol could be successfully incorporated into packaging lms with at least 60% of the added amounts
retained in the lms after production. The release of sesamol from the lm was completed within 25 h at
10 C and 30 C. Despite the fast release, sesamol antioxidant action continued over extended periods for
both linoleic acid and cereal samples. After a year of storage, cereal samples packaged with sesamol lms
were substantially better than those packaged with controlled lms and were comparable with those
packaged with BHT lms in terms of lower hexanal concentration and rancid odours. The incorporation
of sesamol affected the tensile and optical properties of the lms only slightly.
ACKNOWLEDGEMENTS
This work was partly supported by National Research Initiative Grant 2006-35503-17568 from the USDA
Cooperative State Research, Education, and Extension Service Program on Improving Food Quality and Value,
as well as partly supported by a grant from the US Army Natick Research, Development, and Engineering
Laboratory through a grant to Berry Plastics. The authors thank Saikiran Chaluvadi and Vara Prasad Prodduk
for assistance in preparing this paper.
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