Food Packaging and Shelf Life 23 (2020) 100455

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Food Packaging and Shelf Life

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Effect of active packaging with Satureja thymbra extracts on the oxidative T

stability of fried potato chips
Evanthia Choulitoudi, Aglaia Velliopoulou, Dimitrios Tsimogiannis, Vassiliki Oreopoulou*
National Technical University of Athens, School of Chemical Engineering, Laboratory of Food Chemistry and Technology, 5 Iroon Polytechniou, Zografou 15780, Athens,
Greece

A R T I C LE I N FO A B S T R A C T

Keywords: Satureja thymbra extracts, rich in phenolic acids and flavonoids, were obtained through successive extractions
S. thymbra (L.) with ethyl acetate and ethanol, and tested as natural antioxidants to prolong the shelf life of fried potato chips.
Active packaging The extracts were more effective when coated on a laminated film used as active packaging for the chips,
Antioxidant activity compared to spraying them on the surface of the fried product or adding to the frying oil. The increased in-
Fried potato chips
corporation of the ethanol extract, as coating, from 100 to 300 mg total phenols (expressed as gallic acid
Polyphenols
equivalents, GAE)/m2 resulted in increased protection, as evidenced through peroxide values, volatile products,
and oxygen consumption inside the packaging that remained stable for 55 days. Ethyl acetate extract was very
effective up to a concentration of 200 mg GAE/m2, but demonstrated prooxidant activity at higher concentra-
tion. Partial migration of the natural polyphenols to the product was observed.

1. Introduction
Fried potato chips are a popular snack consumed in many countries.
The shelf life or the product amounts up to few weeks or months, while
the main cause of deterioration is the oxidation of lipids absorbed
during frying. According to literature, there have been some attempts to
monitor lipid oxidation during frying and storage of potato chips or
other fried snacks, through the addition of natural antioxidants
(Houhoula, Oreopoulou, & Tzia, 2003; Jaswir, Man, & Kitts, 2000).
During frying, the oil is exposed to elevated temperature, in the
presence of air and moisture, that induce a number of chemical reac-
tions, including oxidation, hydrolysis, and thermal decomposition. As a
consequence, researchers initially attempted to protect the frying oil by
addition of herbs or extracts, and the earlier published works concern
the obtained results in terms of polymerized triglycerides or conjugated
dienes and trienes of the frying oil (Zandi & Gordon, 1999). Jaswir et al.
(2000) observed that in addition to the protection of the frying oil,
natural antioxidants from rosemary, sage and citric acid improved the
taste, flavor and overall acceptance of the fried potato chips. Lalas and
Dourtoglou (2003) and Houhoula et al. (2003) investigated the effect of
rosemary and oregano, respectively, and observed that their addition to
the frying oil resulted in an increase of the induction period and de-
crease of the oxidation rate of the oil absorbed in the chips.
Lolos, Oreopoulou, and Tzia (1999) added oregano extracts to the
fried chips instead of the frying oil and observed that during storage at
accelerated oxidation conditions (63 °C) the protection provided by the
natural antioxidant was comparable to that of tertiary butyl hydro-
quinone (TBHQ) up to the 7th day of storage but inferior as storage was
extended.
Another potent approach is the addition of antioxidants to packa-
ging films, thus creating an active packaging that could protect the
product. Several groups have tried this approach to protect lipid-based
foods. Garces et al. (2003) patented an antioxidant varnish, based on
plant extracts, and Nerín et al. (2006) reported its efficiency on the
stabilization of beef meat. Camo, Beltrán, and Roncalés (2008) used
oregano and rosemary extracts in active polypropylene film to protect
lamb steaks. In a following research Camo, Lorés, Djenane, Beltrán, and
Roncalés (2011) proved that there is a correlation between oregano
extract concentration and antioxidant capacity. Also, Jung et al. (2009);
López de Dicastillo et al. (2011), and used plant extracts in non-edible
films and effectively protected fish products. However, there is no lit-
erature report about the use of active packaging for the protection and
extension of the shelf life of fried snacks.
Therefore, the present study was undertaken in order to evaluate the
effectiveness of active packaging to protect fried potato chips from
quality deterioration and also to compare active packaging with other
ways of using natural antioxidants. Satureja thymbra, a common herb of
the Lamiaceae family, native in Mediterranean countries, was used as

⁎
Corresponding author.
E-mail address: vasor@chemeng.ntua.gr (V. Oreopoulou).

https://doi.org/10.1016/j.fpsl.2019.100455
Received 27 March 2019; Received in revised form 2 December 2019; Accepted 13 December 2019
Available online 19 December 2019
2214-2894/ © 2019 Elsevier Ltd. All rights reserved.
E. Choulitoudi, et al.
the source of natural antioxidants. Extracts of the herb obtained with
food grade solvents, namely ethyl acetate and ethanol were used, since
similar extracts proved effective as antioxidant additives in previous
studies (Choulitoudi et al., 2017; Tsimogiannis et al., 2017). Moreover,
the migration of natural antioxidants from the packaging material to
the product was studied. The results of the present study could poten-
tially be expanded to other fried snacks, to improve their quality.
2. Materials and methods
2.1. Materials
Dried leaves of S. thymbra were obtained from the Agricultural
Research Centre of Northern Greece (member of the Helenic
Agricultural Organisation DEMETER). Palm oil was a product of AGR-
OTIKI SA (Athens, Greece). Potatoes were purchased from the local
market. Gallic acid (98 %, w/w) was a product of Acros Organics (Fair
Lawn, New Jersey, USA). The reagents included Folin – Ciocalteu re-
agent (Merck, Darmstadt, Germany) and sodium carbonate
(Mallinckrodt, St. Louis, Missouri, USA). Water, acetonitrile, and me-
thanol (HPLC and MS grade, Fisher Scientific, Loughborough, UK) were
used for chromatographic analyses, while glacial acetic acid (HPLC
grade, PanReac, Barcelona, Spain) was used for the acidification of
HPLC solvents. A laminated film, oriented polypropylene (OPP) 20 μm/
ink/adhesive/polyethylene terephthalate (PET) metal foil (MET)
12 μm/adhesive/Polyethylene (PE) 75 μm Single trip container (STC),
was obtained from VLACHOS BROS SA (Athens, Greece) and was used
as packaging material for the fried potato chips.
2.2. Production and analysis of the extracts
Ethyl acetate (EAcs) and ethanol (Es) extracts of S. thymbra were
obtained according to Tsimogiannis et al. (2017). Briefly, the dried
leaves of the herb were subjected to water-steam distillation to remove
the essential oil, dried at 38 °C and ground to pass a 0.5 mm sieve. The
ground material (60 g) was extracted in a Soxhlet apparatus, for 6 h,
with ethyl acetate (350 mL) to obtain the EAcs, followed by a sub-
sequent extraction, for 6 h, with ethanol (350 mL) to obtain the Es. The
final extracts were adjusted to a volume of 500 mL, by diluting with the
relevant solvent, and kept in dark bottles until used. The quantification
of total phenols was performed by the Folin – Ciocalteu method
(Waterhouse, 2005) and the results were expressed in gallic acid
equivalents (GAE), through construction of a reference curve. HPLC-
DAD-ESI-MS/MS analysis was performed for the determination of
phenolic compounds, according to the previously documented proto-
cols by Choulitoudi et al. (2016) and Tsimogiannis et al. (2017).
2.3. Experimental procedure
The potatoes were peeled, cut as uniformly as possible (1.1–1.3 mm
thick), washed, kept submerged in water at room temperature for 1 h
maximum, and wiped before use. A domestic-type electric fryer
(Kenwood, model DF SSO, PK OOS/WGR, Havant, UK), of 5.6 L capa-
city was used for the deep-frying process. The fryer was equipped with a
thermostat ( ± 1 °C) and an inert cross - linked steel wire that kept the
potato chips dipped in the oil, but not in contact with the fryer’s inner
surface. The deep fryer was filled with 4.0 kg of refined palm oil, and
successive batches of potatoes (160 ± 10 g) were deep fried at 180 °C,
for 2 min, with an interval of 1 min between fryings, without topping up
the oil. Fresh oil was used for each series of successive fryings.
Two series of experiments were conducted:
In the first series, different ways of extracts addition were tested as
follows: a) 200 g of palm oil were weighed in a spherical flask and the
appropriate volume of EAcs was added so as to reach a concentration of
10,000 mg GAE/kg oil. The organic solvent was removed by means of
vacuum evaporation and N2 purge. Then the solvent-free solution was
2
Food Packaging and Shelf Life 23 (2020) 100455
incorporated into 3.8 kg of palm oil, in the fryer, and mixed thoroughly
to obtain 4 kg of frying oil containing 500 mg GAE/kg oil before
starting the frying experiment (EAcs oil). Es was not tested as additive
to the frying oil because it was not soluble into the oil to give a
transparent solution. b) Either EAcs or Es were uniformly sprayed on
the fried potato chips surface, within an hour from their removal from
the fryer, by using a nozzle (EAcs sprayed and Es sprayed, respectively).
Subsequently the chips were purged with N2 to remove the solvents.
The spayed quantities were adjusted so as to obtain a concentration of
approximately 100 mg GAE/kg oil absorbed in the fried potato chips. c)
Either EAcs or Es were uniformly coated on the packaging material,
(OPP 20 μm/ink/adhesive/PET MET 12 μm/adhesive//PE 75 μm STC)
by using a roll on. A total surface of 2.8 m2 was coated and the quantity
of the extract was adjusted so as to obtain a concentration of 200 mg
GAE/m2 of EAcs (EAcs coated) and of 400 mg GAE/m2 of Es (Es coated).
The packaging was left open for 5 min to evaporate the solvents before
use. d) Additionally a control treatment (Control) without the addition
of any extract was performed.
The packaging material was cut in 0.42 m × 0.21 m, so as to obtain
an internal surface of 0.076 m2 after sealing. Afterwards, a bag was
formed by thermo-sealing the three sides, filled with 25 g of fried potato
chips and, subsequently, the fourth side was thermo-sealed.
In the second series of experiments the extracts were further tested
as coatings of the packaging material at various concentrations. The
samples tested were: Control (Control), EAcs coated on the packaging
material at a concentration of 100, 200 or 300 mg GAE/m2 (EAcs-100,
EAcs-200, EAcs-300, respectively) and Es coated on the packaging
material at a concentration of 100, 200 or 300 mg GAE/m2 (Es-100, Es-
200, Es-300, respectively).
2.4. Accelerated oxidation of the fried potato chips
The packaged samples were placed into an air circulated oven at
70 °C to accelerate oxidation. Duplicate bags of fried potato chips were
removed from the oven at definite time intervals and subjected to
analyses to determine the primary and secondary oxidation products of
the oil absorbed into the chips.
2.5. Determination of volatile products
The volatile products, formed inside the package through the de-
gradation of primary oxidation products were absorbed by a Solid
Phase Micro-Extraction (SPME) apparatus and analysed by Gas
Chromatography – Mass Spectrometry. A SPME needle cartridge, with a
50/30 μm divinylbenzenecarboxen/poly(dimethylsiloxane) fibre (DVB/
CAR/PDMS, Supelco, Sigma-Aldrich Ltd., Dorset, UK) was precondi-
tioned by heating to 230 °C, for 15 min, in the injection inlet of the
GC–MS before use. The samples removed from the oven were kept in
isothermal cabs, at 40 °C, for 30 min before the SPME fiber was inserted
in the headspace of each sample and remained for 30 min, while the
sample was maintained at 40 °C. Following the fiber was retracted into
the needle and immediately transferred to the gas chromatograph. The
SPME needle was then reopened in the injection inlet of the GC–MS.
The analysis was carried out in an Agilent Technologies (Palo Alto,
California, USA) 7890A GC gas chromatograph coupled to an Agilent
Technologies 5975 C MSD mass selective detector, and equipped with
an Agilent HP-5 capillary column (19091J-413, 30 m ×0.25 mm in-
ternal diameter; coating thickness 0.25 μm). He was used as carrier gas,
with a flow rate of 1 mL/min and at a linear velocity of 36 cm/s, and
splitless mode. The temperature of the column was raised from 50 °C to
100 °C at a rate of 10 °C/min and from 100 °C to 220 °C at a rate of
15 °C/min and held at 220 °C for 7 min. Measurements obtained from
the duplicate samples were averaged and the % reduction of each
compound was calculated as:
[(area of compound in control sample – area of compound in the treated
E. Choulitoudi, et al. Food Packaging and Shelf Life 23 (2020) 100455

sample) / area of compound in control sample] * 100 Table 1

The main identified phenolic compounds of S. thymbra extracts.
Compounds EAcs Es
2.6. Measurement of remaining O2 inside the package
concentration on dried extract basis (mg/g)

After the determination of volatile products and before opening the Caffeic acid – 2.25 ± 0.06
packages a measurement of % O2 inside the package was performed by Luteolin 7,4´-di-O-glucuronide – 11.72 ± 0.31
the use of a Gas Analyzer CheckMate 9900 O2/CO2 PBI Dansensor Rosmarinic acid 30.27 ± 0.26 110.68 ± 0.41
Apigenin 7-O-glycoside 0.14 ± 0.01 26.86 ± 0.38
(Ringsted, Denmark). Apigenin diglycoside – 7.08 ± 0.21
Eriodictyol 5.40 ± 0.07 1.83 ± 0.12
2.7. Determination of peroxide value and p-anisidine value Lithospermic acid – 9.09 ± 0.91
Salvianolic acid A 0.21 ± 0.03 6.16 ± 0.75
Naringenina 8.46 ± 0.02 –
After the SPME of the volatile products, the package was opened, Quercetin 1.95 ± 0.04 –
the fried potato chips were ground in a laboratory mill (Retch ZM1; Luteolinb 1.50 ± 0.11 –
Haan, Germany) and mixed with 250 mL of n-hexane for 15 min to Apigeninb 12.76 ± 0.16 5.69 ± 0.22
extract the lipid phase. The hexane was removed through vacuum Carvacrol 22.27 ± 0.33 –
Thymol 17.72 ± 0.25 –
evaporation (Heidolph G1, Schwabach, Germany) at 40 °C and the re-
6-OH Luteolin 7,3´-dimethyl 0.96 ± 0.02 18.69 ± 0.34
maining oil was weighted and further processed for the analysis of etherb
primary and secondary oxidation products. More specifically, peroxide 6-OH Luteolin 7,3´,4´-trimethyl 0.88 ± 0.04 9.83 ± 0.12
value (PV) was determined according to the standard method Cd 8–53 etherb
of American Oil Chemists Society (1998), and p-anisidine value (p-AV) Total phenols on dried extract 131 ± 5.3 233 ± 4.6
basis
according to the standard method Cd 18–90 of American Oil Chemists
Society (1998). Duplicate samples of oil (2 ± 0.1 g) extracted from a
Expressed as eriodictyol equivalents.
each fried potato chips sample were measured, averaged, and the pre- b
Expressed as quercetin equivalents.
sented results are mean values of the averages of duplicate samples
removed from the oven. and mass spectra. EAcs presented four major peaks that were identified
as rosmarinic acid, naringenin, apigenin and carvacrol. Eriodictyol,
2.8. Total phenolic content of the packaging material and of the oil quercetin and luteolin were present, too. These compounds have also
absorbed in the fried potato chips been identified by Skoula and Grayer (2005); Tsimogiannis et al. (2017)
and Choulitoudi et al. (2016). The rest compounds identified in EAcs
The Folin – Ciocalteu method (Waterhouse, 2005) was used for the were minor constituents, as can be seen in Table 1, while their content
quantification of total phenolic content (expressed as GAE) of the was much higher in Es.
packaging material and the oil extracted from the chips. 100 cm2 of the The main compounds identified in Es were rosmarinic acid, salvia-
packaging material was washed with approximately 12 mL of either nolic acid A, luteolin 7,4´-di-O-glucuronide, 6−OH luteolin 7,3´-di-
ethanol or ethyl acetate, depending on the coating, in order to recover methyl ether, 6-OH luteolin 7,3´,4´-trimethyl ether, apigenin and api-
the remaining extract. The washing liquors were placed in a 25 mL genin 7-O-glycoside. Other phenolic acids that were identified were
volumetric flask and diluted to the mark. One sample from each lithospermic acid and caffeic acid. Rosmarinic, lithospermic and sal-
package was used for the analysis and the presented results are mean vianolic acids are well-known caffeic acid derivatives, found in several
values of duplicate packages. plant extracts (Martins et al., 2014; Yuan, Pan, Fu, Makino, & Kano,
The total phenolic content of the oil extracted from fried potato 2005). However, rosmarinic acid is the most abundant one and was the
chips was determined as described by Gutfinger (1981), using a triple main phenolic acid detected in both Es and EAcs extracts.
extraction of a solution of oil in hexane with a methanol:water (80:20) Ethanol recovered the highest quantities of phenolic acids. Overall,
mixture. More specifically, 1 ± 0.05 g of oil was mixed with 10 mL the content of phenolic acids was higher than that of flavonoids in Es,
hexane and the solution was extracted successively with three 20 mL contrary to EAcs. The total phenol content, measured by the Folin
portions of 80 % aqueous methanol. The mixture was shaken each time Ciocalteu method, is also presented in Table 1, and as can be seen the Es
for 2 min. The extracts were combined and processed by the Folin- contained almost two-fold higher phenolic compounds than the EAcs
Ciocalteau assay. Total phenol content was expressed as mg GAE/g oil. extract, mainly due to the much higher content in phenolic acids, but
One measurement was performed for each fried potato chips sample, also to flavonoid derivatives.
and the presented results are mean values of duplicate samples of stored
fried potato chips removed from the oven. 3.2. Comparison of the effectiveness of the extracts in different treatments

2.9. Statistical analysis
Analysis of variance (ANOVA) and Duncan’s multiple range test
were applied to evaluate significant differences among different treat-
ments. Analyses were performed with the STATISTICA software (ver-
sion 10, StatSoft®Inc., United States). Differences were considered to be
significant at p < 0.05.
3. Results and discussion
3.1. Phenolic profile of the extracts
The HPLC-DAD-ESI–MS/MS analysis of the extracts revealed 4–7
main peaks in each extract and several minor ones. Table 1 presents the
components identified in S. thymbra extracts, according to their UV–vis
In the first series of experiments, different ways of the extracts ad-
dition were attempted, as described in the experimental section. More
specifically, the extracts were added a) into the frying oil, b) onto fried
potato chips, and c) as coatings on the packaging material that was
subsequently used to package the fried potato chips. The autoxidation
of fried potato chips was monitored by quantification of the PVs in the
absorbed oil, while the decrease of O2 in the packages during storage
was also measured. The results are presented in Fig. 1a–b.
The absorbed oil in the fried potato chips varied within
0.35 ± 0.02 g/g, with no statistically significant difference among
treatments. All treatments protected fried potato chips against lipid
oxidation, with significant differences among them, observed at 18 days
of storage and onwards. In general, coating of the antioxidants on the
packaging material offered higher protection to the product, followed
by addition to the frying oil and spraying on the fried product, although

3
E. Choulitoudi, et al. Food Packaging and Shelf Life 23 (2020) 100455

Fig. 1. The effect of applying S. thymbra extracts, obtained by ethyl acetate
(EAcs) and ethanol (Es), to the frying oil (EAcs oil), to fried potato chips just
after their removal from the fryer (EAcs sprayed, Es sprayed) and as coatings on
the packaging material (EAcs coated, Es coated) on slowing down the primary
oxidation process during storage at 70 °C (a): Change of peroxide value (PV) of
the oil absorbed in the fried potato chips versus storage time (t) and (b): de-
crease of % O2 in the packaging versus storage time (t) (mean of two different
specimens with two measurements in each ± standard deviation).
Fig. 2. The effect of coating the packaging material with S. thymbra extracts on
slowing down the peroxide value (PV) formation during storage at 70 °C (mean
of two different specimens with two measurements in each ± standard de-
viation). Treatments with (a): ethanol extract at 100, 200 and 300 mg GAE/m2
(Es 100, Es 200, Es 300) and (b): ethyl acetate extract at 100, 200 and 300 mg
GAE/m2 (EAcs 100, EAcs 200, EAcs 300).
3.3. Effect of active packaging with different concentrations of the extracts
on the stability of fried potato chips

differences among the latter treatments were not always significant.

In the second series of experiments the autoxidation of fried potato
More specifically, EAcs oil at a concentration of 500 mg GAE/kg oil
chips was monitored by quantification of both primary and secondary
showed antioxidant activity better than EAcs sprayed but close to Es
products of the oxidation reactions, while the decrease of O2 in the
sprayed. Comparing samples with Es and EAcs, sprayed on chips surface
packages during storage was also measured.
at the same concentration (approximately 100 mg GAE/kg absorbed oil
The PVs of the samples are presented in Fig. 2a–b. Measurements
in chips), Es presented better protection against the oxidation of the
were extended up to 55 days, so as to better estimate differences among
product. However Es, coated on the packaging material at 400 mg GAE/
treatments. In general, after an induction period, the PV increased
m2 showed lower antioxidant protection than EAcs, coated at 200 mg
significantly during storage until the end of the study. The antioxidant
GAE/m2. Es was applied as coating at a higher concentration than EAcs
protection of fried potato chips increased as the concentration of Es
because it contains phenolics of higher polarity and molecular weight,
extract increased up to 300 mg GAE/m2 (Fig. 2a). Similarly, increasing
i.e. phenolic acids and glycosides (Table 1), that were expected to dif-
the concentration of EAcs extract from 100 to 200 mg GAE/m2 en-
fuse more difficultly to the surface of the chips so as to protect the oil.
hanced protection (Fig. 2b). On the contrary, the concentration of EAcs
Nevertheless, the results probably signify that the concentration of
300 mg GAE/m2 showed clear prooxidant activity. However, com-
400 mg GAE/m2 might induce some prooxidant action, as it has been
paring Es and EAcs extracts at the same concentration (100 or 200 mg
observed that natural antioxidants may act as prooxidants at high
GAE/m2), Es exhibited lower protective activity than EAcs that was very
concentrations (Rietjens et al., 2002). Yordi, Pérez, Matos, and Villares
effective in slowing down the primary oxidation process.
(2012) published a list of fourteen phenolic acids, considered to be
As mentioned in Section 3.1, Es contains mainly phenolic acids
antioxidants but under certain conditions behaved as prooxidants.
(rosmarinic, salvianolic and lithospermic), which are active against free
The decrease of %O2 in the packaging, due to its consumption
radicals (Miron, Herrero, & Ibáñez, 2013). Previous experiments in-
through oxidation, was more or less proportional to the increase of PVs,
dicated that the ethanol extract of S. thymbra demonstrated both anti-
as presented in Fig. 1b, thus verifying the above observed results.
microbial and antioxidant activity when incorporated in fish coating
Overall, the results of the addition of natural S. thymbra extracts by
material, which could be mainly attributed to its high content in phe-
different ways indicated that coating of the packaging material, in other
nolic acids (Choulitoudi et al., 2016). Moreover, Ozturk (2012) tested a
words using them in active packaging, was the most promising treat-
methanolic extract of S. thymbra by the β-carotene-linoleic acid and
ment. Therefore we proceeded with further experimentation on active
DPPH radical assay, and found it very effective in both assays. How-
packaging with the aim to find the most effective extract concentrations
ever, the phenolic compounds of Es are polar and may show low affinity
to extend the product shelf life.
for the oil, and consequently lower protection than EAcs. Thus a higher
concentration (300 mg GAE/m2) was proved necessary to scavenge the

4
E. Choulitoudi, et al.
Fig. 3. p-Anisidine value of vegetable oil extracted from fried potato chips
stored at 70 °C (mean of two measurements in two different specimens ±
standard deviation). (Abbreviations are explained in Fig. 2).
peroxyl radicals and protect the oil of the fried potato chips.
The efficient protection observed with EAcs extract can be explained
by the high content of several flavonoids that are potent antioxidants.
Moreover, these are compounds of low polarity and therefore, they
have easy access to the oil absorbed in the chips. The prooxidant effect
of EAcs at 300 mg GAE/m2 may be attributed to flavonoid prooxidant
properties that seem to be concentration – dependent (Rietjens et al.,
2002; Wilms, Kleinjans, Moonen, & Briedé, 2008).
Secondary oxidation products were monitored through p-AV of fried
potatoes oil. The p-AV of all the studied treatments ranged between
10.4 and 18.8, with no significant difference among treatments and
storage time (Fig. 3a–b). These results indicate that no appreciable
amount of aldehydes, which are detectable by the specific method, is
formed during the storage of fried potato chips and consequently p-AV
is not an appropriate index for the estimation of their deterioration. The
p-AV measures mainly the a-alkenals, produced by a specific fission of
the carbon chain of the fatty acids hydroperoxides, i.e. the fission of the
C13-C14 bond of the main hydroperoxide of linoleic acid (9t11t-13-li-
noleic-OOH). Nevertheless, the decomposition of linoleic acid hydro-
peroxides follows the path of C12-C13 bond fission, which leads to the
production of hexanal and a beta-alkenal. The adduct of beta-alkenals
with p-anisidine reagent presents up to fifth fold lower absorbance than
a-alkenals and therefore the overall sensitivity of the method is low
according to the standard method Cd 18–90 of American Oil Chemists
Society (1998).
Additionally, the volatile aldehydes that are formed through sec-
ondary oxidation reactions were measured by SPME-GC/MS. The main
compounds detected were hexanal and nonanal while heptanal and
octanal were also present. Similarly, Damanik and Murkovic (2018)
studied the stability of palm oil during heating in a rancimat apparatus
at 120 °C and the results showed a concentration of 56.8 ppm of hex-
anal, 81.65 ppm of heptanal, 88.75 ppm of octanal and 113.6 ppm of
nonanal, after 6 h. Also, Melton, Jafar, Sykes, and Trigiano (1994)
5
Food Packaging and Shelf Life 23 (2020) 100455
Table 2
Reduction (%) of volatile aldehydes from the headspace of the packaging
coated with ethyl acetate (EAcs) and ethanol (Es) extracts of S. thymbra.
Treatment Hexanal Heptanal Octanal Nonanal
Es 100 10.8 ± 4.6c 34.5 ± 4.9bc 44.7 ± 4.3b 24.8 ± 6.4bc
Es 200 26.0 ± 6.2bc 54.9 ± 5.1a 56.5 ± 6.3b 36.8 ± 5.6b
Es 300 29.8 ± 5.7bc 46.8 ± 6.6ab 82.6 ± 8.4a 56.9 ± 5.7a
EAcs 100 42.5 ± 5.5b 13.3 ± 4.4d 48.2 ± 5.2b 27.7 ± 5.6b
EAcs 200 68.6 ± 4.8a 18.2 ± 4.9cd 53.7 ± 6.1b 7.6 ± 2.5cd
EAcs 300 −13.9 ± 6.7d −44.3 ± 7.1e 51.0 ± 5.7b −7.0 ± 2.7d
a-d
Different superscripts in the same column indicate significant differences
(p < 0.05).
reported that potatoes fried in palm oil, rich in oleic acid, had high
concentration of octanal, nonanal and decanal. The palm oil used in the
present study had a high content of oleic (42.99 %), and palmitic (41.39
%) and a lower of linoleic (10.38 %) acid. Choe and Min (2006) found
that the oxidation of oleic acid led to the production of octanal and
nonanal, while linoleic acid in hexanal and heptanal among other
secondary products.
Nonanal is probably produced by the breakdown of oleate 9-OOH,
while hexanal from linoleate 13-OOH, as mentioned above.
Additionally, octanal probably originated by the decomposition of
oleate 11-OOH, and heptanal from linoleate 11-OOH (Morales, Rios, &
Aparicio, 1997). Therefore the high content of nonanal is justified by
the high content of oleic acid in the palm oil used. The high con-
centration of hexanal is in agreement with the fact that linoleic acid is
20–40 times more susceptible to oxidation than oleic acid. In general,
the content of volatiles remained low until 12 days and increased
afterwards. Table 2 presents the % reduction of volatile aldehydes
(compared to the control sample) in the headspace of the packaging,
after 55 days of storage at 70 °C (end of storage period). As can be seen,
the reduction increased as the concentration of Es extract increased up
to 300 mg GAE/m2. Similarly, increasing the concentration of EAcs
extract from 100 to 200 mg GAE/m2 enhanced protection against the
production of heptanal and octanal. On the contrary, the % reduction of
nonanal and hexanal decreased, but their content did not exceed that of
control samples. The concentration of 300 mg GAE/m2 showed clear
prooxidant activity, in accordance with the results obtained for primary
oxidation (PVs).
The decrease of O2 content in the packaging, due to its consumption
through oxidation, was in agreement with the aforementioned results
(Fig. 4a–b). More specifically, the higher the concentration of Es ex-
tract, the lower the decrease of O2 in the packaging. Similarly, in-
creasing the concentration of EAcs extract from 100 to 200 mg GAE/m2
delayed the decrease of O2. On the contrary, the concentration of
300 mg GAE/m2 showed the highest decrease of O2 among all experi-
ments, including control samples.
3.4. Changes of the phenolic compounds within the package during storage
Fig. 5a–b presents the reduction of the phenolic compounds content
of the packaging material coated by the Es and EAcs extracts during
storage. The reduction rate for both extracts was higher as the coating
concentration increased. The loss of phenolic compounds should be
mainly attributed to their participation in oxidation reactions, which is
desired in order to protect the fried potatoes from oxidation. However,
part of them might have migrated to the product through contact with
the packaging material. In order to create a material for use in an active
packaging application, transfer of the antioxidant must be allowed to
take place between the packaging and the food. The antioxidant should
migrate on the surface or into the food product, where it can help to
inhibit oxidation, thereby extending the shelf life of the product
(Ganiari, Choulitoudi, & Oreopoulou, 2018).
The total phenolic content of the oil extracted from the fried potato
E. Choulitoudi, et al.
Fig. 4. The decrease of O2 content (%) in the packaging versus storage time (t),
at 70 °C (mean of two different specimens ± standard deviation).
(Abbreviations are explained in Fig. 2).
Fig. 5. Reduction of the phenolic compounds content, expressed as gallic acid
equivalents (GAE)/m2 of the packaging material coated with (a): ethanol ex-
tract and (b): ethyl acetate extract during storage of the samples at 70 °C (mean
of two different specimens ± standard deviation). (Abbreviations are ex-
plained in Fig. 2).
chips is presented in Fig. 6a–b. The highest level was determined for all
the studied treatments at the first storage days and indicated the pro-
gressive transfer of phenolic compounds from the packaging material to
6
Food Packaging and Shelf Life 23 (2020) 100455
Fig. 6. Change of the total phenolic content (mg GAE/g) of the oil extracted
from fried potato chips versus storage time (t) (mean of two different speci-
mens ± standard deviation). (Abbreviations are explained in Fig. 2).
the product. After that, the phenolic content reduced until the end of
the study, due to participation in oxidation reactions, protecting the
lipid substrate. As expected, the phenolic content was higher as the
coating concentration increased, and, in consequence, coatings with
higher contents of total phenols resulted in higher levels of these sub-
stances in the fried chips and hence in higher antioxidant protection.
Comparing Es and EAcs extracts at the same concentration, Es exhibited
lower values than EAcs, probably because the nonpolar compounds of
EAcs extract can be transferred easier to the oil of fried chips than the
polar compounds of Es extract. The release of active substances from
the packaging material and their migration to food depends on the af-
finity of the antioxidants substances for the food matrix (López-de-
Dicastillo et al., 2012). Thus, at low concentration, EAcs was more ef-
fective in slowing down the oxidation process than Es.
The migration of a small portion of the natural phenolic anti-
oxidants from the packaging material to the product may be beneficial
for the consumers, since phenolic compounds possess several health
promoting effects (Boudet, 2007). They exhibit a wide range of phy-
siological properties such as antimicrobial, antioxidant, anti-throm-
botic, cardioprotective and vasodilatory effects (Manach, Mazur, &
Scalbert, 2005; Middleton, Kandaswami, & Theoharides, 2000). Various
rosmarinic acid-containing extracts from the leaves of herbs and spices
have been reported to possess antioxidant, antimutagenic, anti-tu-
morigenic, anti-HIV, anti-proliferative, and anti-cyclooxygenase prop-
erties (Kelm, Nair, Strasburg, & DeWitt, 2000; Makino et al., 2000).
4. Conclusions
Extracts from S. thymbra can be effectively used for the protection of
fried potato chips against oxidation. Addition of these natural anti-
oxidants to the packaging material, results in active packaging that is
favorable in delaying the deterioration of the fried product, compared
E. Choulitoudi, et al.
to adding the extracts to the frying oil or the fried product. S. thymbra
extracts are rich in phenolic compounds (phenolic acids and flavonoids)
and their antioxidant properties depend on their concentration on the
packaging material. Prooxidant phenomena may be observed as the
concentration of flavonoids exceeds certain levels.
Author statement
Evanthia Choulitoudi: Conseptualization, methodology, formal
analysis, writing-original draft preparation.
Aglaia Velliopoulou: Investigation, data curation.
Dimitrios Tsimogiannis: Methodology, validation, resourses.
Vassiliki Oreopoulou: Supervision, writing-reviewing & editing.
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